JP2007041237A - Method of manufacturing color filter, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing color filter capable of improving the contrast of a liquid crystal display device, without causing orientation disorder of liquid crystal. <P>SOLUTION: The method of manufacturing color filter comprises a step of providing a photosensitive resin composition for orientation-controlling protrusions; performing relative scanning, while modulating light in accordance with image data by using spatial light modulation devices two-dimensionally arrayed; and thereby, forming an orientation-controlling protrusion image. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter manufacturing method, a color filter, and a liquid crystal display device, and more particularly to a color filter manufacturing method in which alignment control protrusions are formed by laser exposure or the like without using a mask, and a color filter manufactured by the method. Liquid crystal display device with filter

  In recent years, a liquid crystal display (LCD) has been most widely used as a flat panel display to replace a CRT (Cathode-Ray Tube) display, and its expectation is also great. Among them, the thin film transistor (TFT) type LCD (TFT-LCD) is expected to further expand the market by application to personal computers, word processors, OA devices, portable televisions, etc. There is a need for further improvement in image quality.

  Currently, the most widely used method among TFT-LCDs is a normally white mode TN (Twisted Nematic) type LCD. However, the TN type LCD has a drawback that the viewing angle is narrow, and the display state differs depending on the position where the display screen is observed. For this reason, the TN type LCD has a problem that its application is limited.

  The problem with TN-type LCDs is that they can be displayed by holding a liquid crystal between a pair of substrates with electrodes and applying a voltage between the electrodes (for example, a simple matrix type or a plasma addressed type LCD). This is also a problem that occurs in the same way.

  That is, such an LCD can be seen almost white in any orientation in a white display state where no voltage is applied. However, in a black display state in which a predetermined voltage is applied, obliquely incident light passes obliquely with respect to liquid crystal molecules aligned in the vertical direction. For this reason, when the black display LCD is observed from an oblique direction, the light direction is twisted to some extent, so that it looks halftone (gray) instead of being completely black.

  Further, in the halftone display state where an intermediate voltage is applied, the liquid crystal display rises halfway in the middle portion of the cell, and the light that is vertically incident is displayed in halftone (gray). However, in the state of halftone display, the appearance of light incident obliquely on the left and right differs depending on the incident direction. Specifically, since the liquid crystal molecules are aligned in parallel with respect to the light traveling from the lower right to the upper left, the LCD looks black when viewed from the left side. On the other hand, since the liquid crystal molecules are vertically aligned with respect to the light traveling from the lower left to the upper right, when the LCD is observed from the right side, it appears to be almost white. As described above, the LCD described above has a drawback that the display state depends on the viewing angle.

  As a means for solving the above-described drawbacks, a technique for forming protrusions on the liquid crystal layer has been proposed. Such protrusions are formed to control the alignment of the liquid crystal and are referred to as liquid crystal alignment control protrusions. The protrusions locally incline the alignment state of the liquid crystal molecules along the surface, and even when observed obliquely with respect to the liquid crystal surface, the same display state as when the liquid crystal surface is observed from the front To widen the viewing angle.

  As such a technique, a technique of forming a liquid crystal alignment control protrusion using a phenol novolac resin has been proposed (see, for example, Patent Document 1). In this method, the entire surface of the coating layer is exposed using a mask. However, in the case of a liquid crystal alignment control protrusion formed by such a method, the shape of the protrusion may be angular, and as a result, the liquid crystal alignment is disturbed. As a result, there is a problem that the contrast of the liquid crystal display device is lowered.

JP 2002-122858 A

  An object of the present invention is to provide a color filter manufacturing method capable of improving the contrast of a liquid crystal display device without causing disturbance in the liquid crystal alignment, a color filter manufactured by the method, and a liquid crystal display including the color filter. It is to provide an elemental device.

The present invention can solve the above-described problems by the following configuration.
That is, the present invention provides a <1> color filter substrate with a photosensitive resin composition for alignment control protrusions, and modulates light based on image data using a spatial light modulation device arranged in two dimensions. And a step of curing the alignment control projection image by performing relative scanning while performing the relative scanning.
<2> The method of applying the photosensitive resin composition for protrusions for orientation control includes a transfer step of transferring a photosensitive transfer material having at least one photosensitive resin layer on a temporary support to a substrate. <1> The method for producing a color filter according to <1>.
<3> The method for producing a color filter according to <1> or <2>, wherein the alignment control photosensitive resin composition for protrusions includes a naphthoquinonediazide derivative.
<4> The method for producing a color filter according to any one of <1> to <3>, wherein the alignment control photosensitive resin composition for protrusions includes a phenol resin.
<5> A color filter formed by the method for producing a color filter according to any one of <1> to <4>.
<6> A liquid crystal display device having the color filter according to <5>.

  According to the present invention, a method for producing a color filter capable of improving the contrast of a liquid crystal display device without causing disturbance in the liquid crystal alignment, a color filter produced by this method, and a liquid crystal display provided with this color filter An elemental device can be provided.

  The method for producing a color filter of the present invention is a method of applying a photosensitive resin composition for alignment control protrusions and using a spatial light modulation device arranged in two dimensions to perform relative scanning while modulating light based on image data. And a step of curing by exposure for forming a two-dimensional image.

In this invention, it exposes with respect to the layer which consists of the photosensitive resin composition for protrusions for orientation control. The exposed photosensitive resin composition layer may be formed by applying to a substrate or the like, or may be formed by a transfer method using a transfer material.

  Locations of the liquid crystal alignment control protrusions in the liquid crystal display device will be described with reference to FIG. FIG. 19 is a schematic view showing a liquid crystal display device using liquid crystal alignment control protrusions. 19A, the liquid crystal display device 10 has a structure in which a glass substrate 12, a conductive layer 14, a liquid crystal layer 16 including liquid crystal molecules 15, a conductive layer 18, and a glass substrate 20 are stacked in this order. Have. In FIG. 19A, the liquid crystal alignment control protrusion 22 can be provided between the conductive layer 14 and the liquid crystal layer 16 and between the conductive layer 18 and the liquid crystal layer 16. Further, as shown in FIG. 19B, when the liquid crystal display device 10 has a color filter 24 between the conductive layer 18 and the glass substrate 20, the liquid crystal alignment control protrusions 22 are also formed as shown in FIG. As shown in b), it can be provided between the conductive layer 18 and the liquid crystal layer 16 and between the conductive layer 14 and the liquid crystal layer 16. A liquid crystal alignment film (polyimide film) may be provided between the liquid crystal alignment control protrusion 22 and the liquid crystal layer 16.

  Hereinafter, the photosensitive transfer material used in the present invention, and the liquid crystal alignment control protrusion and the liquid crystal display device formed using the same will be described in detail.

<Photosensitive transfer material>
The photosensitive transfer material used in the present invention has at least one photosensitive resin layer, and may have a thermoplastic resin layer and an intermediate layer as necessary. Hereinafter, the photosensitive transfer material used in the present invention will be described taking an example in which a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer are laminated in this order on a temporary support. However, the present invention is not limited to this, and may be an embodiment in which a photosensitive resin layer is formed directly on the temporary support, or between the temporary support and the photosensitive resin layer. Only one of the plastic resin layer and the intermediate layer may be formed.

<Photosensitive resin layer>
The photosensitive resin layer preferably contains a cresol resin and a phenol resin, and further preferably contains a naphthoquinone diazide ester as necessary. Further, a high-boiling solvent as a plasticizer and a residual solvent, and other additions An agent can be included. The phenol novolac resin and the like may be known resins, and examples thereof include those described in JP-A-6-308722, JP-A-8-272091, JP-A-6-14888, and JP-A-6-194727. be able to.

(Cresol resin)
The cresol resin preferably has a molar ratio of formaldehyde to cresol of about 0.7 to 1.0, more preferably 0.8 to 1.0. Moreover, as a mass average molecular weight of the said cresol resin, 800-8000 are preferable and 1000-6000 are especially preferable.

  The isomer ratio (molar ratio of o-isomer / m-isomer / p-isomer) of the cresol resin is not particularly limited, but the ratio of p-isomer to all isomers is 10 mol% or more from the viewpoint of improving developability. It is preferable that it is 20 mol% or more. Further, from the viewpoint of improving the liquid crystal panel performance (such as anti-seizing ability), the m-isomer ratio is preferably 5 mol% or more, and preferably 20 mol% or more.

  The said cresol resin may be used independently and can also be used as a 2 or more types of mixture. In this case, you may mix and use other resin, such as a phenol resin. In the present invention, a cresol resin derivative such as a reaction product with naphthoquinone diazide sulfonate may be used as the cresol resin.

  The amount of the cresol resin used is preferably 0.1 to 10 g / m @ 2, more preferably 0.5 to 5 g / m @ 2.

(Naphthoquinone diazide ester)
It is preferable to use naphthoquinone diazide ester together with a cresol resin in the photosensitive resin layer. The naphthoquinone diazide ester may be a monofunctional compound, a bifunctional or higher compound, and a mixture thereof. The monofunctional naphthoquinone diazide ester is preferably an ester compound obtained by reacting naphthoquinone-4-sulfonic acid chloride or naphthoquinone-5-sulfonic acid chloride with a substituted phenol.

  The bifunctional or higher naphthoquinone diazide ester is preferably an ester compound obtained by reacting naphthoquinone-4-sulfonic acid chloride or naphthoquinone-5-sulfonic acid chloride with a compound having a plurality of phenolic hydroxyl groups. Examples of the compound having a plurality of phenolic hydroxyl groups include polyphenols such as bisphenols, trisphenols and tetraquinosphenols; polyfunctional phenols such as dihydroxybenzene and trihydroxybenzene; bis-type or tris-type dihydroxybenzene or Trihydroxybenzene, asymmetric polynuclear phenol, a mixture thereof, and the like are preferable.

  Specific examples of the compound having a phenolic hydroxyl group include, for example, 4-t-butylphenol, 4-isoamylphenol, 4-t-octylphenol, 2-isopropyl-5-methylphenol, 2-acetylphenol, and 4-hydroxybenzophenone. , 3-chlorophenol, 4-benzyloxycarbonylphenol, 4-dodecylphenol, resorcinol, 4- (1-methyl-1-phenylethyl) -1,3-benzenediol, phloroglucinol, 4,4′-dihydroxy Benzophenone, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) methane, 2,3,4,4′- Tetrahydroxybenzophenone, 4,4 ' [(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], and the like.

  Specific examples of the naphthoquinonediazide ester include, for example, 4′-t-octylphenylnaphthoquinonediazide-4-sulfonate, 4′-t-octylphenylnaphthoquinonediazide-5-sulfonate, 4′-benzoylphenylnaphthoquinonediazide-5 Sulfonate, reaction product of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,3,4,4′-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5 -Reaction products with sulfonic acid chloride. These may be used alone or in combination of two or more.

  The mass ratio of the naphthoquinone diazide ester to the cresol resin in the photosensitive resin is preferably 1 to 200% by mass and more preferably 5 to 50% by mass from the viewpoint of improving developability.

(Other additives)
In order to promote the developability of the photosensitive resin layer, the photosensitive resin layer may contain a divalent or higher aliphatic carboxylic acid or a divalent to hexavalent phenol compound. Examples of the divalent or higher aliphatic carboxylic acid include malonic acid, succinic acid, fumaric acid, maleic acid, hydroxysuccinic acid, glutaric acid, and adipic acid, and malonic acid and succinic acid are preferable. As content of the said bivalent or more aliphatic carboxylic acid with respect to the total solid in the said photosensitive resin, 0.5-20 mass% is preferable, and 5-15 mass% is still more preferable.

  Moreover, as said 2-6 valent phenol compound, a 2-4 valent phenol compound is especially preferable. Examples of the divalent to hexavalent phenol compound include resorcinol, 4- (1-methyl-1-phenylethyl) -1,3-benzenediol, phloroglucinol, 4,4′-dihydroxybenzophenone, bis (4 -Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) methane, 2,3,4,4'-tetrahydroxybenzophenone, 4 , 4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol] and the like, and resorcinol and 1,1-bis (4-hydroxyphenyl) cyclohexane are preferable. As content of the said 2-6 valent phenol compound with respect to the total solid in the said photosensitive resin, 0.5-20 mass% is preferable, and 5-15 mass% is still more preferable.

  Furthermore, a decolorizable dye may be added to the photosensitive resin layer from the viewpoint of enabling recognition of failures such as transfer failure and accuracy failure during the formation of the liquid crystal alignment control protrusions and improving manufacturing suitability. it can. The decolorizable dye generally means a pigment that can be decolored by heating at 200 ° C. for 1 hour, and is a colored dye that can be decolored during baking. As the decolorizable dye, a dye that can be decolored by heating at 180 ° C. for 1 hour is preferable. Such dyes usually undergo structural changes due to thermal decomposition or oxidation, or are evaporated or sublimated by heat. In addition, when a liquid crystal alignment control protrusion is produced using a decolorizable dye, the liquid crystal alignment control protrusion has a light transmittance of 90% or more with respect to parallel light of 400 to 800 nm after decoloring. Is preferred.

  Examples of the decolorizable dye include dyes that decompose by heat, such as dialkylaminotriphenyl such as Victoria Pure Blue BOH, Victoria Pure Blue BOH-M, Malachite Green, Eisen Malachite Green, Malachite Green Hydrochloride, Eisen Diamond Green, and the like. Examples include methane-based dyes. Examples of the dye that evaporates or sublimates by heat include Orient Oil Brown, Methyl Yellow, Sumicaron Brilliant Blue B, 1,3,5-triphenyltetrazolium formazan, and the like.

  As the decolorizable dye, in addition to the above, the stain resistance evaluation of the sublimation fastness test described in Dye Handbook (edited by Synthetic Organic Chemistry Association, Maruzen, issued July 20, 1972) (180 ° C., Those having a condition of 1 to 3 hours) can also be used. Specifically, CI Disperse Yellow 8, 31, 72, CI Disperse Orange 1, 3,20, 21, CI Disperse Red 15, 55, 60, 65, CIDisperse Violet 8, 23,26, 37, CI Disperse Blue 20, 26, 55, 56, 72, 90, 91, 92, 106, CI Disperse Black 29, Diacellition Direct Black BM / D (Mitsubishi Kasei Co., Ltd.), Sumikaron Violet RS (Sumitomo Chemical Co., Ltd.), Examples include Dianix Fast Sky Blue BM / D (Mitsubishi Kasei Co., Ltd.), Miketon Polyester Blue BCL, GRN (Mitsui Petrochemical Co., Ltd.), Kayaron Polyester Navy Blue GF (Nippon Kayaku Co., Ltd.), and the like. Considering the suitability of the heating device and environmental pollution, the decolorizable dye is preferably a thermally decomposable dye.

  The addition amount of the decolorizable dye is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin layer.

  Moreover, a thermoplastic binder can be used for the photosensitive resin layer. Examples of the thermoplastic binder include known binders such as ethylenically unsaturated compounds. The addition amount of the binder and the plasticizer is appropriately determined as long as the effects of the present invention are not impaired.

(Photosensitive resin layer)
The photosensitive transfer material of the present invention is a positive transfer material that uses a cresol resin and a naphthoquinone diazide ester in combination with a photosensitive resin layer to remove the exposed portion by development with an aqueous alkaline solution when exposed in a desired pattern. It can be a photosensitive transfer material. That is, naphthoquinone diazide ester acts as a dissolution inhibitor for alkali-soluble cresol resins, but when it receives light, it produces indenecarboxylic acid and the dissolution-inhibiting effect is lost. For this reason, the said photosensitive resin layer containing a cresol resin and a naphthoquinone diazide functions as a positive resist in which only a light irradiation part is melt | dissolved by alkali image development.

  The layer thickness of the photosensitive resin layer is preferably 0.5 to 10 μm, and more preferably 1 to 6 μm. When the film thickness is in the range of 0.5 to 10 μm, when the photosensitive resin layer coating solution is applied onto the temporary support, pinholes are unlikely to occur, and the exposed portion can be easily removed for development. Can be done.

  The photosensitive resin layer comprises a photosensitive resin composition in which components contained in the photosensitive resin layer such as the cresol resin and naphthoquinonediazide ester described above are dissolved in a solvent, a temporary support (a temporary support and a photosensitive resin layer, and In the case where a thermoplastic resin layer or an intermediate layer is provided between the layers, it can be formed by applying and drying on the layer) using various application means.

  As a solvent used for the said photosensitive resin composition, what was selected from the well-known solvent suitably can be used in the range which does not impair the effect of this invention. Examples of the solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve acetate Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as tilether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3- And esters such as methyl methoxypropionate, ethyl 3-methoquinpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate; and the like. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these, in terms of solubility of each component and film forming property, ketones such as methyl ethyl ketone, glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, 2-hydroxypropionic acid Particularly suitable are esters such as ethyl, methyl 3-methoxypropionate and ethyl 3-ethoxypropionate, and diethylene glycols such as diethylene glycol dimethyl ether.

  As the coating means for forming the photosensitive resin layer, a known coating means can be appropriately selected.

<Temporary support>
As the temporary support, those having a releasability that does not interfere with transfer with respect to a thermoplastic resin layer described later are preferable, and those that are chemically and thermally stable and flexible are preferable. Specific examples of the temporary support include a thin film sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, and polypropylene, or a laminate thereof.

  Between the temporary support and the thermoplastic resin layer, it is preferable that surface treatment such as glow discharge is not performed and an undercoat layer such as gelatin is not provided in order to ensure good peelability. As thickness of the said temporary support body, 5-300 micrometers is suitable and 20-150 micrometers is preferable.

  It is preferable that the photosensitive resin layer has a high oxygen transmission rate. In order to increase the oxygen transmission rate of the photosensitive resin layer, it is desirable to use a resin having low crystallinity and a low glass transition temperature, and an additive for plasticizing the resin may be added.

<Thermoplastic resin layer>
The thermoplastic resin layer is provided as the first layer on the temporary support and mainly contains a thermoplastic resin, and may contain other components as necessary. As the above-mentioned thermoplastic resin, alkali development after transfer is possible, or removal processing is possible when the thermoplastic resin protrudes to the surroundings and contaminates the substrate to be transferred depending on the transfer conditions at the time of transfer. Therefore, a resin that is soluble in an alkaline aqueous solution is preferable. Furthermore, the thermoplastic resin layer prevents transfer defects that may occur due to convex portions existing on the substrate (or on the color filter) when transferring onto the substrate (or on the color filter) that is the transfer target. From the viewpoint of also exerting the function as a cushioning material, it is preferable that it has a property that it can be deformed according to the convex portion of the surface of the transfer object during heat adhesion.

  In view of the above, the thermoplastic resin is preferably an alkali-soluble resin having a substantial softening point of 80 ° C. or lower. Examples of thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth). Examples include saponified products such as saponified products with acrylic acid ester copolymers, poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers of butyl (meth) acrylate and vinyl acetate. The thermoplastic resin may be a single type or a combination of two or more types.

  Further, the thermoplastic resin has a softening point of about 80 as described in “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, issued on October 25, 1968). Among organic polymer substances having a temperature of 0 ° C. or lower, those soluble in an alkaline aqueous solution can be used.

  In addition, even when an organic polymer substance has a softening point of 80 ° C. or higher, a substantial softening point can be obtained by adding various known plasticizers compatible with the organic polymer substance to the organic polymer substance. The temperature can be lowered to 80 ° C. or lower.

  When the organic polymer substance is used, various polymers, supercooling substances, adhesion improvers, interfaces, and the like within a range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support described above. An activator, a release agent and the like can also be added.

  The photosensitive transfer material of the present invention can be formed by sequentially laminating a later-described intermediate layer and the photosensitive resin layer on the temporary support, in addition to the thermoplastic resin layer. It is necessary that the adhesive strength between the temporary support and the adhesive strength between other layers be smaller. Thereby, after transfer, the temporary support can be easily peeled off, and further, the temporary support can be removed without being accompanied by destruction of the surface of the thermoplastic resin layer. This is a preferable aspect in that the exposure to the photosensitive resin layer after removing the temporary support can be performed uniformly.

  The thermoplastic resin layer is prepared by dissolving a thermoplastic resin and other components as required in an organic solvent to prepare a coating solution (a coating solution for a thermoplastic resin layer). It can be formed by coating or the like by a coating method.

  Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as rumethyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone Class: ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3 -Esters such as methyl methoxypropionate, ethyl 3-methopropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate; and the like. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these, in terms of solubility of each component and film forming property, ketones such as methyl ethyl ketone, glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, 2-hydroxypropionic acid Particularly suitable are esters such as ethyl, methyl 3-methoxypropionate and ethyl 3-ethoxypropionate, and diethylene glycols such as diethylene glycol dimethyl ether.

  Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added.

  As a layer thickness of the said thermoplastic resin layer, 6-100 micrometers is preferable and 6-50 micrometers is more preferable. When the layer thickness is in the range of 6 to 100 μm, convex portions of 1 μm or more on the substrate (or color filter) can be completely absorbed, and developability and production suitability can be improved.

<Intermediate layer>
Since an organic solvent is used for the photosensitive resin layer and the thermoplastic resin layer, both intermediate layers have a function of preventing the two layers from being mixed with each other. Moreover, the said intermediate | middle layer should just be disperse | distributed or melt | dissolved in water or aqueous alkali solution.

  The intermediate layer is mainly composed of a resin component that can be dispersed and dissolved in water or an aqueous alkali solution, and may contain other components such as a surfactant, if necessary. The resin component constituting the intermediate layer can be appropriately selected from known ones. For example, the polyvinyl ether / maleic anhydride polymer described in JP-A No. 46-2121 and JP-B No. 56-40824 is disclosed. , Water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, Examples thereof include ethylene oxide polymers, water-soluble salts of the group consisting of various starches and the like, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof.

Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable, and an additive may be further added. Further, the polyvinyl alcohol preferably has a saponification rate of 99% or less, particularly preferably 90% or less. Moreover, as content of the said polyvinylpyrrolidone, it is preferable that it is 1-75 mass% of solid content of an intermediate | middle layer, It is more preferable that it is 1-60 mass%, It is most 10-50 mass% preferable. Adhesiveness with the photosensitive resin layer can be sufficiently enhanced when the content of the polyvinyl pyrrolidone is in the range of 1 to 75% by mass.
As the additive, those that plasticize the resin component to be used are preferable, glycerin, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and their monoether, diether, monoester, diester, monoamide, And diamide compounds. The addition amount of the additive is preferably 0 to 30% by mass of the resin, and more preferably 1 to 20% by mass.

The intermediate layer is formed by dissolving and dispersing a resin component or the like in an aqueous solvent to prepare a coating liquid (intermediate layer coating liquid) and coating the coating liquid on the thermoplastic resin layer by a known coating method. Is possible.
Examples of the aqueous solvent include a solvent containing water such as distilled water as a main component and, if desired, a solvent having affinity with water such as alcohol, a salt, or the like as long as the effects of the present invention are not impaired.

  The thickness of the intermediate layer is preferably about 0.1 to 5 μm, and more preferably 0.5 to 2 μm. When the layer thickness is between 0.1 and 5 μm, layer mixing of the thermoplastic resin layer and the photosensitive resin layer does not occur, and development and intermediate layer removal can be easily performed.

<Surface protection film>
A surface protective film is provided on the photosensitive resin layer for the purpose of protecting it from dirt and damage during storage. The surface protective film can be easily affixed to the photosensitive resin layer, and can be selected from those easily peelable from the photosensitive resin layer, and is made of the same or similar material as the temporary support. May be. Specifically, silicone paper, polyolefin, polytetrafluoroethylene sheet or the like is preferable, and among them, polyethylene and polypropylene films are more preferable. Furthermore, it is preferable that there are 1000 or more recesses with a depth of 0.3 μm or more per cm 2 on the surface of the surface protective film in contact with the photosensitive resin layer, and there are 5000 or more recesses with a depth of 0.3 μm or more per cm 2. More preferred. The recess may be formed by embossing the film, may be formed by matting (sand blasting), or may be smoothed by etching. These can be produced by the method described in JP-A-1-110930. The number of recesses on the surface protective film surface can be measured by observing with an optical microscope.
In addition, the depth of the concave portion on the surface protective film surface is the distance from the center plane average height to the deepest portion of each concave portion, and after first obtaining the central plane average height, the depth to the deepest portion of each concave portion It can be determined by measuring the distance. Specifically, it can be measured by a laser microscope, a surface roughness shape measuring machine (Surfcom; manufactured by Tokyo Seimitsu Co., Ltd.), or the like.

  As thickness of the said surface protection film, about 5-100 micrometers is preferable and 10-60 micrometers is more preferable.

<Method for producing photosensitive transfer material>
The photosensitive transfer material used in the present invention is obtained by first applying a coating solution (a coating solution for a thermoplastic resin layer) prepared by dissolving a thermoplastic resin in a solvent onto the temporary support, and drying the thermoplastic resin. Next, a coating solution (intermediate layer coating solution) using a solvent that does not dissolve the thermoplastic resin layer is applied on the thermoplastic resin layer, and dried to provide an intermediate layer. It can be formed by applying a coating solution prepared by dissolving cresol resin or the like in a solvent that does not dissolve the intermediate layer (photosensitive resin layer coating solution) and drying to provide a photosensitive resin layer. Alternatively, a photosensitive resin layer is provided on the surface protective film, and a thermoplastic resin layer and an intermediate layer are separately provided on a temporary support, and the intermediate layer and the photosensitive resin layer are bonded to each other. Can also be formed. In addition, the photosensitive transfer material used in the present invention is provided with a photosensitive resin layer and an intermediate layer on the surface protective film, and separately provided with a thermoplastic resin layer on a temporary support, respectively, It can manufacture by bonding together so that an intermediate | middle layer and the photosensitive resin layer may contact | connect.

  Further, as described later, after the photosensitive transfer material used in the present invention is adhered to a substrate or a color filter which is a transfer target, in the process of peeling the temporary support of the photosensitive transfer material, As a result of the substrate and the like being charged, the surrounding dust or the like may be attracted, and the dust or the like may adhere to the photosensitive resin layer after peeling. In such a case, an unexposed portion may be formed in the photosensitive resin layer in the subsequent exposure process, and the portion may remain during development. For this reason, for the purpose of preventing electrification, by providing a conductive layer on at least one surface of the temporary support or using a temporary support with conductivity, the electrical resistance of the surface is reduced to 1013 Ω or less. It is preferable to reduce.

  In order to impart conductivity to the temporary support as described above, a conductive substance may be contained in the temporary support. As such a method, for example, a method of kneading metal oxide fine particles or an antistatic agent in advance is suitable. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and crystalline oxides such as molybdenum oxide and / or composite oxides thereof. Fine particles are mentioned.

  Examples of the antistatic agent include Electro Stripper A (manufactured by Kao Corporation), Elenon No. Alkyl phosphate anionic surfactants such as 19 (Daiichi Kogyo Seiyaku Co., Ltd.); Betaine amphoteric surfactants such as Amorgen K (Daiichi Kogyo Seiyaku Co., Ltd.); Nissan Nonion L (Nippon Yushi Polyoxyethylene fatty acid ester-based nonionic surfactants such as Emulgen 106, 120, 147, 420, 220, 905, 910 (made by Kao Corporation) and Nissan Nonion E (made by Nippon Oil & Fats Co., Ltd.) Polyoxyethylene alkyl ether type nonionic surfactants such as) are suitable. Other nonionic surfactants include polyoxyethylene alkylphenol ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, and the like.

  When the conductive layer is provided on the temporary support, the conductive layer can be appropriately selected from known ones. As the conductive material used for the conductive layer, at least one crystalline metal oxide selected from ZnO, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO, MoO3, and / or a composite oxide thereof Fine particles. A method in which these conductive substances are contained in a conductive layer and used is preferable in that a stable conductive effect is exhibited without being affected by the humidity environment.

  The volume resistance value of the crystalline metal oxide or the composite oxide fine particles is preferably 10 7 Ω · cm or less, more preferably 10 5 Ω · cm or less. Moreover, as the particle diameter, 0.01-0.7 micrometer is preferable and 0.02-0.5 micrometer is still more preferable.

  A method for producing fine particles of the crystalline metal oxide and its composite oxide is described in detail in JP-A-56-143430. That is, firstly, metal oxide fine particles are produced by firing and heat treatment is performed in the presence of different atoms to improve conductivity, and secondly, the conductivity is improved when producing metal oxide fine particles by firing. And a third method for introducing oxygen defects by reducing the oxygen concentration in the atmosphere when producing metal fine particles by firing. Specific examples of the hetero atom include Al, In, etc. for ZnO; Nb, Ta, etc. for TiO 2; and Sb, Nb, halogen elements, etc. for SnO 2. .

  As addition amount of the said different atom, 0.01-30 mol% is preferable and 0.1-10 mol% is more preferable. The amount of conductive particles used is preferably 0.05 to 20 g / m @ 2, more preferably 0.1 to 10 g / m @ 2.

  In the conductive layer provided on the temporary support of the photosensitive transfer material of the present invention, as a binder, for example, gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, etc. Cellulose esters; homopolymers or copolymers containing vinylidene chloride, vinyl chloride, styrene, acrylonitrile, vinyl acetate, alkyl acrylates having 1 to 4 carbon atoms, vinyl pyrrolidone, etc .; soluble polyesters, polycarbonates, soluble polyamides, etc. may be used it can.

  In addition, when dispersing conductive particles in these binders, a dispersion such as a titanium-based dispersant or a silane-based dispersant may be added, and a binder cross-linking agent may be added as necessary. it can.

  Examples of the titanium dispersant include titanate coupling agents, preneact (manufactured by Ajinomoto Co., Inc.) and the like described in US Pat. Nos. 4,069,192 and 4,080,353. Is mentioned. Examples of the silane dispersant include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. "Silane coupling agent" (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the binder crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and an epoxy crosslinking agent.

The conductive layer is prepared by dispersing conductive fine particles in a binder and coating the temporary support or applying a subbing treatment (for example, an undercoat layer) on the temporary support. It can be provided by attaching.

  The conductive layer may be provided on the surface of the temporary support opposite to the surface on which the photosensitive resin layer is coated. In this case, the conductive layer is formed on the conductive layer for the purpose of ensuring sufficient scratch resistance. It is preferable to further provide a hydrophobic polymer layer. The hydrophobic polymer layer may be applied in a state where the hydrophobic polymer is dissolved in an organic solvent or in the form of an aqueous latex, and the coating amount is preferably about 0.05 to 1 g / m @ 2 in terms of dry mass.

  Examples of the hydrophobic polymer include cellulose esters such as nitrocellulose and cellulose acetate; vinyl polymers containing vinyl chloride, vinylidene chloride, vinyl acrylate and the like; polymers such as organic solvent-soluble polyamide and polyester.

  For the purpose of imparting smoothness to the hydrophobic polymer layer, for example, a smoothing agent such as an organic carboxylic acid amide described in JP-A-55-79435 can be used. Moreover, a mat agent etc. can also be used as needed. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer is not substantially affected.

  When an undercoat layer is provided, JP-A-51-135526, U.S. Pat. Nos. 3,143,421, 3,586,508, 2,698,235, No. 3,567,452 etc., vinylidene chloride copolymer described in JP-A No. 51-114120, US Pat. No. 3,615,556 etc. Glycidyl acrylate or glycidyl methacrylate-containing copolymers described in JP-A-51-58469, polyamide / epichlorohydrin resins described in JP-A-48-24923, and JP-A-50-39536 A maleic anhydride-containing copolymer can be used.

  In the present invention, JP-A-56-82504, JP-A-56-143443, JP-A-57-104931, JP-A-57-118242, JP-A-58-62647, A conductive layer described in JP-A-60-258541 can be used as necessary.

When the conductive layer is applied on the temporary support, it can be applied by a known method such as roller coating, air knife coating, gravure coating, bar coating, or curtain coating. In order to obtain a sufficient antistatic effect, the surface electrical resistance value of the conductive layer or the temporary support provided with conductivity is preferably 10 ¹³ Ω or less, and more preferably 10 ¹² Ω or less. .

  In addition, in order to prevent strong adhesion between the thermoplastic resin layer and the temporary support, a slip agent composition containing known fine particles, a release agent composition containing a silicone compound, etc. are applied to the temporary support surface. You can also.

  When a conductive layer is provided on the surface of the temporary support on which the thermoplastic resin layer is not provided, the temporary support is provided with, for example, a glow layer for the purpose of improving the adhesion between the thermoplastic resin layer and the temporary support. Surface treatment such as discharge treatment, corona treatment, ultraviolet irradiation treatment, undercoating treatment such as phenolic substance, polyvinylidene chloride resin, styrene butadiene rubber, gelatin, or a combination of these treatments can be applied.

  The film for the temporary support can be formed by extrusion, but when a conductive material or a conductive layer is contained in the same or different plastic raw material as the temporary support and is extruded simultaneously with the film. Can easily obtain a conductive layer excellent in adhesion and scratch resistance. In this case, it is not necessary to provide the hydrophobic polymer layer or the undercoat layer, and this is the most preferred embodiment as a conductivity-imparting temporary support constituting the transfer material.

<Pattern formation method using photosensitive transfer material>
Then, the pattern formation method of this invention is demonstrated. Here, as a photosensitive transfer material used in the present invention, a photosensitive transfer material in which an alkali-soluble thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a surface protective film are laminated in this order on a temporary support. Furthermore, an example using a substrate provided with a color filter layer on the entire surface of the substrate is shown.

  First, the surface protective film of the photosensitive transfer material used in the present invention is removed, and the photosensitive resin layer is intimately bonded onto a substrate as a transfer target under pressure and heating. For the bonding of the substrate and the heat-sensitive recording layer, one appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to increase productivity.

At this time, in the pattern forming method of the present invention, it is preferable to laminate a photosensitive transfer material containing at least one naphthoquinonediazide derivative. The method of laminating the photosensitive transfer material includes heating the substrate in advance before laminating, increasing the roll temperature of the laminator during lamination, and the substrate transport speed when passing through the laminator during lamination. There are ways to slow down.
In the method of heating the substrate in advance before laminating, the substrate temperature is preferably 80 ° C. or higher and 180 ° C. or lower, and more preferably 100 ° C. or higher and 130 ° C. or lower. In order to heat the substrate, a contact heater such as a hot plate can be used in contact with the substrate, or it can be used in a non-contact manner. Further, a non-contact type heater such as a hot air heater or an IR heater can be used in a non-contact manner. If the substrate temperature is lower than 120 ° C, pixels may be chipped after pattern formation. If the substrate temperature exceeds 180 ° C, the material in the photosensitive transfer material may be decomposed, resulting in a change in sensitivity or coloring. .
In the method of raising the laminator roll temperature during lamination, the roll temperature is preferably 80 ° C. or higher and 160 ° C. or lower, and more preferably 80 ° C. or higher and 130 ° C. or lower. If the roll temperature is less than 80 ° C, pixels may be chipped after pattern formation. If the roll temperature exceeds 160 ° C, the material in the photosensitive transfer material is decomposed, causing a sensitivity change, coloring, etc. Wrinkles may occur between the transfer material and the substrate.

  In the method of slowing the substrate conveyance speed when passing through the laminator during lamination, the conveyance speed is preferably 1.0 m / min or more and 10 m / min or less, and 1.2 m / min or more and 5 m / min or less. It is more preferable. If the conveyance speed is less than 1.0 m / min, there is no problem in performance, but a decrease in productivity may be a problem, and if it exceeds 10 m / min, pixel missing may occur after pattern formation.

  Moreover, in the pattern formation method of this invention, the board | substrate heating process which heats the board | substrate which transferred the said photosensitive transfer material between the transfer process of transferring a photosensitive transfer material to a board | substrate, and the exposure process of exposing with a desired pattern. It is preferable to contain. In this case, the photosensitive transfer material may or may not contain a naphthoquinonediazide derivative. The step of heating the substrate to which the photosensitive transfer material has been transferred can be used by bringing a contact-type heater such as a hot plate into contact with the substrate, or can be used in a non-contact manner. Further, a non-contact type heater such as a hot air heater or an IR heater can be used in a non-contact manner. The step of heating the substrate to which the photosensitive transfer material has been transferred is preferably performed in a temperature range of 120 ° C. to 180 ° C. and in a time range of 20 seconds to 120 seconds, and in a temperature range of 120 ° C. to 150 ° C. for 20 seconds. It is more preferable to carry out within a time range of from 50 seconds to 50 seconds. If the temperature is less than 120 ° C. or less than 20 seconds, pixel defects may occur after pattern formation. If the temperature exceeds 180 ° C., the material in the photosensitive transfer material may be decomposed, resulting in a change in sensitivity or coloring. In addition, if it exceeds 120 seconds, a decrease in productivity may be a problem.

After transferring the photosensitive transfer material to the substrate and before exposing with a desired pattern, the temporary support is peeled off at the interface with the thermoplastic resin layer, but the step of heating the substrate to which the photosensitive transfer material has been transferred is You may carry out before peeling off a temporary support body, and you may carry out after peeling off a temporary support body.

  Furthermore, in the pattern forming method of the present invention, the heat of the photosensitive resin layer is transferred between a transfer step of transferring a photosensitive transfer material containing at least one naphthoquinonediazide derivative to a substrate and an exposure step of exposing with a desired pattern. It is preferable to include a step of removing the plastic resin layer and the intermediate layer. The step of removing the thermoplastic resin layer and the intermediate layer of the photosensitive resin layer can be performed by a known method, and a solvent or an aqueous solution that dissolves the thermoplastic resin layer and the intermediate layer and does not dissolve the photosensitive resin layer. Using a developer, particularly an alkaline aqueous solution, for example, (a) immersing the exposed substrate itself in a developing bath, (b) spraying the exposed substrate by spraying, etc. For the purpose of enhancing the solubility, it can be carried out while rubbing with a rotating brush or a wet sponge or by irradiating ultrasonic waves. As the alkaline aqueous solution, a dilute aqueous solution of an alkaline substance is preferable, and a solution to which a small amount of a water-miscible organic solvent is added can also be suitably used. Examples of the alkaline substance include alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal silicates such as sodium silicate and potassium silicate, and metasilicic acid. Examples include alkali metal metasilicates such as sodium and potassium metasilicate, triethanolamine, diethanolamine, monoethanolamine, and trisodium phosphate.

After transferring the photosensitive transfer material to the substrate and before exposing with a desired pattern, the temporary support is peeled off at the interface with the thermoplastic resin layer, but the thermoplastic resin layer and the intermediate layer of the photosensitive transfer material are removed. The step of removing is preferably performed after peeling off the temporary support.

  The method of laminating the photosensitive transfer material, the method of heating the substrate having the photosensitive transfer material transferred between the transfer step and the exposure step, and the thermoplasticity of the photosensitive resin layer between the transfer step and the exposure step. The method for removing the resin layer and the intermediate layer may be performed independently or in combination.

  As described above, the photosensitive transfer material is laminated and / or the substrate on which the photosensitive transfer material is transferred between the transfer process and the exposure process, and / or between the transfer process and the exposure process. If there is a thermoplastic resin layer and an intermediate layer after removing the thermoplastic resin layer and the intermediate layer of the photosensitive transfer material, the thermoplastic resin layer and the intermediate layer are passed through the thermoplastic resin layer and the intermediate layer from above. When there is no plastic resin layer and intermediate layer, the photosensitive resin layer is subjected to positive exposure (patterning) from above the photosensitive resin layer.

  Next, the patterning method of the present invention includes an exposure step of forming a two-dimensional image by using a spatial light modulation device arranged in two dimensions to perform relative scanning while modulating light based on image data. .

  Hereinafter, this exposure process will be described.

(Definition of maskless exposure)
The maskless exposure of the present invention may also be called maskless pattern exposure. An object called a `` mask '' that forms an image (exposure pattern, also referred to as a pattern) with a material that does not transmit the exposure light or weakly transmits it is placed in the optical path of the exposure light, and the photosensitive layer corresponds to the image. This is an exposure method in which a photosensitive layer is exposed in a pattern without using the above-mentioned “mask”, compared to a conventional exposure method in which the pattern is exposed (referred to as mask exposure).
More specifically, the maskless exposure of the present invention can be referred to as exposure for forming a two-dimensional image by performing relative scanning while modulating light based on image data.

(Description of light source)
In the maskless exposure of the present invention, an ultrahigh pressure mercury lamp or a laser is used as a light source.
An ultra-high pressure mercury lamp is a discharge lamp in which mercury is sealed in a quartz glass tube, etc., and has a high vapor pressure of mercury to improve luminous efficiency (the mercury vapor pressure during lighting is about 5 MPa) W. Elenbaas: Light Sources, Philips Technical Library 148-150). It is. Of the bright line spectrum, i-line (365 nm), h-line (405 nm), and g-line (436 nm) are used, with 365 nm being mainly used.

Laser, an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplifying and oscillating light waves, utilizing the phenomenon of stimulated emission that occurs in materials with an inverted distribution. There are crystals, glass, liquid, dye, gas, etc. as excitation media. Solid laser (YAG laser), liquid laser, gas laser (argon laser, He-Ne laser, carbon dioxide laser, excimer laser), semiconductor laser from these media A known laser such as can be used.

A semiconductor laser uses a light emitting diode that induces coherent light at a pn junction when electrons and holes flow out to the junction due to carrier injection, electron beam excitation, collision ionization, photoexcitation, etc. It is. The wavelength of the emitted coherent light is determined by the semiconductor compound.
The wavelength of the laser is not particularly limited. However, from the viewpoint of resolution, cost of the laser device, and availability, it is preferable to select a semiconductor laser from a wavelength range of 300 to 500 nm, but 340 to 450 nm is more preferable. 405 nm is particularly preferable.
For solid-state lasers, the YAG-SHG solid-state laser at 532 nm can be mentioned. Furthermore, 532, 355, and 266 nm can be cited for semiconductor-excited solid-state lasers, and 355 nm is preferably selected from the viewpoint that conventional photopolymerization initiators for resists have sensitivity.
In the gas laser, a KrF laser of 249 nm and an ArF laser of 193 nm are used.
Among these light sources, considering the case where the photosensitive material is exposed in the manufacturing process of the display device, it is preferable to select a light source having an exposure wavelength of 410 nm from the viewpoint of increasing the transmittance of the display region. .

A method of relative scanning while modulating light according to the present invention will be described.
One typical method is a two-dimensional micromirror such as DMD (digital micromirror device, for example, an optical semiconductor developed by Dr. Larry Hornbeck et al. In 1987 in Texas Instruments). This is a method of using spatial modulation elements arranged in line.
In this case, the light from the light source is irradiated onto the DMD by an appropriate optical system, and the reflected light from each mirror arranged two-dimensionally on the DMD passes through another optical system and the like on the photosensitive layer in a two-dimensional manner. An image of light spots arranged in a row is formed. If the light spot is not exposed between the light spots, the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction. The entire surface of the photosensitive layer can be exposed in such a manner that the light spots in the rear row are exposed between the light spots. An image pattern can be formed by controlling the angle of each mirror of the DMD and turning the light spot on and off. By aligning and using such exposure heads having DMD, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but 256 gradation exposure can be performed by using a mirror gradation spatial modulation element.

  On the other hand, another representative method of relative scanning while modulating light according to the present invention is a method using a polygon mirror. A polygon mirror is a rotating member that has a series of flat reflective surfaces around it. The light from the light source is reflected and irradiated onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. An image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. By using a plurality of light from the light source, the scanning time can be shortened.

As a method of performing relative scanning while modulating light of the present invention, for example, the following method can also be applied.
An example of drawing using a polygon mirror described in Japanese Patent Laid-Open No. 5-150175, an apparatus using a polygon mirror by visually acquiring a part of an image of a lower layer described in JP-T-2004-523101 (WO2002 / 039793) In this example, exposure is performed with the position of the upper layer aligned with the position of the lower layer, an example of exposure with DMD described in JP-A-2004-56080, an exposure apparatus equipped with a polygon mirror described in JP-T-2002-523905, and JP-A-2001-255661. An exposure apparatus including a polygon mirror described in JP-A-2003-50469, an example of a combination of DMD, LD, and multiple exposure described in JP-A-2003-50469, an example of an exposure method that changes an exposure amount depending on a part of a substrate described in JP-A-2003-156893, This is an example of an exposure method for performing misalignment adjustment described in Japanese Patent Application Laid-Open No. 2005-43576.

Hereinafter, the relative scanning exposure will be described in detail.
(Relative scanning exposure)
The exposure method of the present invention includes a method using an ultrahigh pressure mercury lamp and a method using a laser, but the latter is preferred.
As the laser used in the present invention, known lasers such as an argon laser, a He—Ne laser, a semiconductor laser, a carbon dioxide gas laser, and a YAG laser can be used.
The wavelength of the laser is not particularly limited, but in particular, it is selected from the wavelength range of 300 to 500 nm from the viewpoint of the resolution of the image pattern (for example, alignment control protrusion), the cost of the laser device, and the availability. Although preferably 340 to 450 nm, more preferably 405 nm.
The beam diameter of the laser is not particularly limited, but among them, from the viewpoint of the resolution of the image pattern (for example, alignment control protrusion), the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, more preferably 7 to 20 μm. .
Although it does not specifically limit as energy amount of a laser beam, From a viewpoint of exposure time and resolution, 1-100 mJ / cm < ² > is preferable especially and 5-20 mJ / cm < ² > is more preferable.
In the present invention, it is necessary to spatially modulate laser light according to image data. For this purpose, it is preferable to use a digital micro device which is a spatial light modulation element.

  As the exposure apparatus, for example, exposure can be performed using the following apparatus.

An example of a three-dimensional exposure apparatus using laser light is shown below, but the exposure apparatus in the present invention is not limited to this.
As shown in FIG. 1, the exposure unit includes a flat stage 152 that holds the glass substrate 150 by adsorbing the glass substrate 150 to the surface. Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-like installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The exposure apparatus is provided with a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the photosensitive material 150 are provided on the other side. The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 2 and 3B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in an approximately matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the photosensitive material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Therefore, as the stage 152 moves, a strip-shaped exposed area 170 is formed for each exposure head 166 in the photosensitive material 150. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed areas 170 are arranged without gaps in the direction orthogonal to the sub-scanning direction. In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice here). Therefore, can not be exposed portion between the exposure area 168 ₁₁ in the first row and the exposure area 168 _12, it can be exposed by the second row of the exposure area 168 ₂₁ and the exposure area 168 ₃₁ in the third row.

Each of the exposure heads 166 _{11 to} 166 _mn is a spatial light modulator that modulates an incident light beam for each pixel according to image data, as shown in FIGS. 4, 5 (A) and (B). A digital micromirror device (DMD) 50 is provided. The DMD 50 is connected to a controller (not shown) including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input image data. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the image data processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 including a laser emitting portion in which an emitting end portion (light emitting point) of an optical fiber is arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order.

  The lens system 67 includes a pair of combination lenses 71 that collimate the laser light emitted from the fiber array light source 66 and a pair of combination lenses that correct the light quantity distribution of the collimated laser light to be uniform. 73 and a condensing lens 75 that condenses the laser light whose light intensity distribution is corrected on the DMD. With respect to the arrangement direction of the laser emitting end, the combination lens 73 spreads the light beam at a portion close to the optical axis of the lens and contracts the light beam at a portion away from the optical axis, and with respect to a direction orthogonal to the arrangement direction. Has a function of allowing light to pass through as it is, and corrects the laser light so that the light quantity distribution is uniform.

  Further, on the light reflection side of the DMD 50, lens systems 54 and 58 that form an image of the laser light reflected by the DMD 50 on the scanning surface (exposed surface) 56 of the photosensitive material 150 are arranged. The lens systems 54 and 58 are arranged so that the DMD 50 and the exposed surface 56 are in a conjugate relationship.

  As shown in FIG. 6, the DMD 50 is configured such that a micromirror 62 is supported by a support column on an SRAM cell (memory cell) 60, and a large number of (pixels) (pixels) are formed. For example, the mirror device is configured by arranging 600 × 800 micromirrors in a lattice pattern. Each pixel is provided with a micromirror 62 supported by a support column at the top, and a material having a high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and is entirely monolithic (integrated type). ).

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is inclined within a range of ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. FIG. 7A shows a state in which the micromirror 62 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 62 is tilted to −α degrees in the off state. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 as shown in FIG. 6 according to the image signal, the light incident on the DMD 50 is reflected in the inclination direction of each micromirror 62. .

  FIG. 6 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. On / off control of each micromirror 62 is performed by a controller (not shown) connected to the DMD 50. A light absorber (not shown) is arranged in the direction in which the light beam is reflected by the micromirror 62 in the off state.

  Further, it is preferable that the DMD 50 be arranged with a slight inclination so that the short side thereof forms a predetermined angle θ (for example, 1 ° to 5 °) with the sub-scanning direction. 8A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 8B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.

In the DMD 50, a number of micromirror arrays in which a large number (for example, 800) of micromirrors are arranged in the longitudinal direction are arranged in a large number (for example, 600 sets) in the short direction. As shown, by tilting the DMD 50, the pitch P ₁ of the scanning trajectory (scan line) of the exposure beam 53 by each micromirror becomes narrower than the pitch P ₂ of the scanning line when the DMD 50 is not tilted, greatly increasing the resolution. Can be improved. On the other hand, since the tilt angle of the DMD 50 is very small, the scan width W ₂ when the DMD 50 is tilted and the scan width W ₁ when the DMD 50 is not tilted are substantially the same.

  Further, the same scanning line is overlapped and exposed (multiple exposure) by different micromirror rows. In this way, by performing multiple exposure, it is possible to control a minute amount of the exposure position and to realize high-definition exposure. Further, joints between a plurality of exposure heads arranged in the main scanning direction can be connected without a step by controlling a very small amount of exposure position.

  Note that the same effect can be obtained by arranging the micromirror rows in a staggered manner by shifting the micromirror rows by a predetermined interval in a direction orthogonal to the sub-scanning direction instead of inclining the DMD 50.

  As shown in FIG. 9A, the fiber array light source 66 includes a plurality of (for example, six) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. Yes. The other end of the multimode optical fiber 30 is coupled with an optical fiber 31 having the same core diameter as the multimode optical fiber 30 and a cladding diameter smaller than the multimode optical fiber 30, as shown in FIG. A laser emission portion 68 is configured by arranging emission ends (light emission points) of the optical fiber 31 in a line along a main scanning direction orthogonal to the sub-scanning direction. As shown in FIG. 9D, the light emitting points can be arranged in two rows along the main scanning direction.

  As shown in FIG. 9B, the emission end of the optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. Further, a transparent protective plate 63 such as glass is disposed on the light emitting side of the optical fiber 31 in order to protect the end face of the optical fiber 31. The protective plate 63 may be disposed in close contact with the end surface of the optical fiber 31 or may be disposed so that the end surface of the optical fiber 31 is sealed. The light emitting end portion of the optical fiber 31 has a high light density and is likely to collect dust and easily deteriorate. However, by disposing the protective plate 63, it is possible to prevent the dust from adhering to the end face and to delay the deterioration.

  Here, in order to arrange the output ends of the optical fibers 31 with a small cladding diameter in a line without any gaps, the multi-mode optical fibers 30 are stacked between two adjacent multi-mode optical fibers 30 at a portion with a large cladding diameter. The exit ends of the optical fibers 31 coupled to the stacked multi-mode optical fibers 30 are the two exit ends of the optical fibers 31 coupled to the two adjacent multi-mode optical fibers 30 in the portion where the cladding diameter is large. They are arranged so that they are sandwiched between them.

  For example, as shown in FIG. 10, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. Here, the multimode optical fiber 30 and the optical fiber 31 are step index optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 25 μm, NA = 0.2, and transmission of the incident end face coating. The ratio is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 25 μm, and NA = 0.2.

  In general, in laser light in the infrared region, propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, more preferably 60 μm or less. Preferably, it is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

  The laser module 64 includes a combined laser light source (fiber light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, which are arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have a common oscillation wavelength (for example, 405 nm), and all the maximum outputs are also common (for example, 100 mW for a multimode laser and 30 mW for a single mode laser). As the GaN semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 nm to 450 nm may be used.

  As shown in FIGS. 12 and 13, the above-described combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and a wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 13, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens 17 is numbered among the plurality of collimator lenses. is doing.

  FIG. 14 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 14).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having an emission width of 2 μm, and each of the laser beams B1 with a divergence angle in a direction parallel to or perpendicular to the active layer being, for example, 10 ° and 30 °. A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Accordingly, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. Each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 20 is obtained by cutting an area including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. The condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

Next, the operation of the exposure apparatus will be described.
In each exposure head 166 of the scanner 162, laser beams B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  Here, a condensing optical system is configured by the collimator lenses 11 to 17 and the condensing lens 20, and a multiplexing optical system is configured by the condensing optical system and the multimode optical fiber 30. That is, the laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has low output, so a desired output cannot be obtained unless multiple rows are arranged. Since the light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled one-on-one, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, as described above, the output of about 1 W can be obtained with the six multimode optical fibers, and the area of the light emitting region at the laser emitting unit 68 is 0.0081 mm ² (0.325 mm × 0.025 mm). Therefore, the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 80 times compared to the conventional case. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared with the conventional one.

  Here, with reference to FIGS. 15A and 15B, the difference in the depth of focus by the exposure head will be described. In FIG. 15A, the diameter of the light emission region of the bundled fiber light source of the exposure head in the sub-scanning direction is 0.675 mm. In FIG. 15B, the light emission region of the fiber array light source of the exposure head in the sub-scanning direction. The diameter is 0.025 mm. As shown in FIG. 15A, in this exposure head, since the light emitting area of the light source (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 increases, and as a result, the light beam incident on the scanning surface 5. The angle becomes larger. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 15B, in this exposure head, since the diameter of the light emitting region of the fiber array light source 66 is small in the sub-scanning direction, the angle of the light beam that passes through the lens system 67 and enters the DMD 50 is small. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. DMD is a reflective spatial modulation element, but FIGS. 15A and 15B are developed views for explaining the optical relationship.

  Image data corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This image data is data representing the density of each pixel constituting the image by binary values (whether or not dots are recorded).

  The stage 152 that has adsorbed the photosensitive material 150 to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the photosensitive material 150 is detected by the detection sensor 164 attached to the gate 160 when the stage 152 passes under the gate 160, the image data stored in the frame memory is sequentially read out for a plurality of lines. A control signal is generated for each exposure head 166 based on the image data read by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micro mirror of the DMD 50 is in an on state forms an image on the exposed surface 56 of the photosensitive material 150 by the lens systems 54 and 58. Is done. In this way, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the photosensitive material 150 is exposed in pixel units (exposure area 168) that is approximately the same number as the number of pixels used in the DMD 50. Further, when the photosensitive material 150 is moved at a constant speed together with the stage 152, the photosensitive material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is formed for each exposure head 166. It is formed.

  As shown in FIGS. 16A and 16B, in the DMD 50, 600 sets of micromirror rows in which 800 micromirrors are arranged in the main scanning direction are arranged in the sub-scanning direction. Thus, only a part of the micro mirror rows (for example, 800 × 100 rows) is controlled to be driven.

  As shown in FIG. 16A, a micromirror array arranged at the center of the DMD 50 may be used, and as shown in FIG. 16B, the micromirror array arranged at the end of the DMD 50 is used. May be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror rows. Get faster. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

  For example, when only 300 sets are used in 600 micromirror rows, modulation can be performed twice as fast per line as compared to the case of using all 600 sets. Further, when only 200 sets of 600 micromirror arrays are used, modulation can be performed three times faster per line than when all 600 sets are used. That is, an area of 500 mm in the sub-scanning direction can be exposed in 17 seconds. Further, when only 100 sets are used, modulation can be performed 6 times faster per line. That is, an area of 500 mm in the sub-scanning direction can be exposed in 9 seconds.

  The number of micromirror rows to be used, that is, the number of micromirrors arranged in the sub-scanning direction is preferably 10 or more and 200 or less, and more preferably 10 or more and 100 or less. Since the area per micromirror corresponding to one pixel is 15 μm × 15 μm, when converted to the use area of DMD50, an area of 12 mm × 150 μm or more and 12 mm × 3 mm or less is preferable, 12 mm × 150 μm or more and 12 mm A region of × 1.5 mm or less is more preferable.

  If the number of micromirror rows to be used is within the above range, as shown in FIGS. 17A and 17B, the laser light emitted from the fiber array light source 66 is made into substantially parallel light by the lens system 67, and the DMD 50 Can be irradiated. It is preferable that the irradiation area where the laser beam is irradiated by the DMD 50 coincides with the use area of the DMD 50. When the irradiation area is wider than the use area, the utilization efficiency of the laser light is lowered.

  On the other hand, the diameter of the light beam condensed on the DMD 50 in the sub-scanning direction needs to be reduced according to the number of micromirrors arranged in the sub-scanning direction by the lens system 67, but the number of micromirror rows to be used. Is less than 10, it is not preferable because the angle of the light beam incident on the DMD 50 increases and the depth of focus of the light beam on the scanning surface 56 becomes shallow. Further, the number of micromirror rows to be used is preferably 200 or less from the viewpoint of modulation speed. DMD is a reflective spatial modulation element, but FIGS. 17A and 17B are developed views for explaining the optical relationship.

  When the sub scanning of the photosensitive material 150 by the scanner 162 is completed and the rear end of the photosensitive material 150 is detected by the detection sensor 164, the stage 152 is moved along the guide 158 by the driving device (not shown) on the most upstream side of the gate 160. Returned to the origin at the point, and again moved along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  As described above, the exposure unit (exposure apparatus) includes a DMD in which 600 micromirror arrays in which 800 micromirrors are arranged in the main scanning direction are arranged in 600 sets in the subscanning direction. Since the control is performed so that only the micromirror array is driven, the modulation speed per line becomes faster than when all the micromirror arrays are driven. This enables high-speed exposure.

  Next, after the above exposure step, development processing is performed, and when there is a thermoplastic resin layer and an intermediate layer, unnecessary portions of the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer (exposed portion in the case of positive) are removed. When there is no thermoplastic resin layer and intermediate layer, unnecessary portions (exposed portion in the case of positive) of the photosensitive resin layer are removed. Then, only an unirradiated part (in the case of a positive type) remains on the conductive layer, and a pattern is formed.

  The development can be performed by a known method, for example, using a solvent or an aqueous developer, particularly an alkaline aqueous solution, for example, (a) immersing the exposed substrate itself in a developing bath, (b) the exposed substrate. For the purpose of further improving the solubility, for example, by spraying with a spray or the like, rubbing with a rotating brush, a wet sponge or the like, or applying ultrasonic waves.

  As the alkaline aqueous solution, a dilute aqueous solution of an alkaline substance is preferable, and a solution to which a small amount of a water-miscible organic solvent is added can also be suitably used. Examples of the alkaline substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, silica Alkali metal silicates such as sodium silicate and potassium silicate, alkali metal metasilicates such as sodium metasilicate and potassium metasilicate, tetraalkyl such as triethanolamine, diethanolamine, monoethanolamine, morpholine and tetramethylammonium hydroxide Ammonium hydroxides, trisodium phosphate and the like can be mentioned.

  The concentration of the alkaline substance in the alkaline aqueous solution is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the water-miscible organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, Examples include acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. The addition amount of the organic solvent is preferably 0.1 to 30% by mass.

  Various known surfactants can also be added to the alkaline aqueous solution. The concentration of the surfactant is preferably 0.01 to 10% by mass. The temperature during development is usually preferably around room temperature to 40 ° C. Furthermore, after the development processing, a step of washing with water can be added.

  When forming the alignment control protrusions and part of the spacers using the photosensitive transfer material of the present invention, the pattern can be further cured by performing a heat treatment called baking after exposure and development. Further, by baking, the pattern shape can be moderately smoothed by pattern shrinkage and appropriate flow.

  The baking temperature is preferably 200 to 300 ° C, more preferably 220 to 260 ° C, and most preferably 230 to 250 ° C. The baking time is preferably 10 to 120 minutes, more preferably 20 to 70 minutes, and most preferably 30 to 60 minutes. Thus, by performing the said baking by setting temperature and time, the crosslinking reaction in a photosensitive resin component can advance easily, discoloration of a color filter can be prevented, and productivity can be improved.

《Alignment control protrusions》
For patterns such as alignment control protrusions (hereinafter also referred to as “liquid crystal alignment control protrusions”), the photosensitive resin layer of the photosensitive transfer material used in the present invention is transferred onto the substrate as described above (transfer process). After the transfer, the photosensitive resin layer can be formed by irradiating the photosensitive resin layer with a pattern (patterning step) and removing an unnecessary portion (exposed portion) by a development process.
The liquid crystal alignment control protrusion formed as described above has a shape and form that can regulate the orientation direction of the liquid crystal molecules, and as described above, inside the conductive layer of the liquid crystal display device (the conductive layer and the liquid crystal layer). The shape and form are not particularly limited. The shape of the liquid crystal alignment control protrusion can be appropriately selected from known shapes. For example, a pyramid shape (triangular pyramid, quadrangular pyramid, etc.) or hemispherical shape with the substrate surface (or color filter surface) as the bottom surface is used. , A conical, trapezoidal, or bowl-shaped one with the substrate surface (or color filter surface) as the bottom surface, or a cross section formed on the substrate (or color filter) in a band shape and perpendicular to the length direction A triangular prism shape having a triangular shape, and a columnar body such as a semicircular shape, a quadrangular shape, a trapezoidal shape, and a bowl shape having a cross-sectional shape orthogonal to the length direction can be used. The liquid crystal alignment control protrusions can be formed in, for example, the shape described in Japanese Patent No. 2947350.

  Further, the arrangement mode of the alignment control protrusions can be appropriately selected from known modes, and for example, can be formed in the mode described in Japanese Patent No. 2947350. For example, a plurality of columnar bodies formed in a strip shape on a substrate and having a trapezoidal cross-sectional shape perpendicular to the length direction are arranged in a pattern extending in parallel in one direction at an equal pitch, and each conductive material of two substrates It may be an embodiment formed between both the layer and the substrate (see FIG. 14 of Japanese Patent No. 2947350). When the liquid crystal alignment control protrusion of the present invention is provided between the conductive layer substrates of both substrates, it is not always necessary to form a structure with the same shape, but a combination of structures with different shapes is formed. Also good. Further, the liquid crystal alignment control protrusion formed in a strip shape on the substrate (or color filter) is not limited to a linear shape, and may be provided in a bent shape at a predetermined angle (Japanese Patent No. 2947350). 42 and 55 etc.).

  In addition, for details on the size, arrangement interval, arrangement shape, etc. of the liquid crystal alignment control protrusions, the description in Japanese Patent No. 2947350 can be referred to.

  Among the above pattern shapes, a pattern having a trapezoidal shape or a trapezoidal shape in cross section perpendicular to the substrate is preferable in that a sufficient viewing angle can be obtained, and the above substrate surface (or color filter surface) is the bottom surface. A trapezoidal shape, a trapezoidal shape, a columnar body having a semicircular shape, a trapezoidal shape, a vertical shape, and the like, which are formed on a substrate (color filter) in a strip shape and perpendicular to the length direction thereof are preferable.

A part of the spacer can also be formed using the photosensitive transfer material used in the present invention. In this case, for example, at the time of forming the color filter, a part where two or more kinds of pixel materials of the color filter overlap is formed, and after forming the transparent electrode, the photosensitive transfer material used in the present invention is formed thereon. A part of the spacer can be formed by transferring the photosensitive resin layer.
The thickness of the spacer generally needs to be equal to the cell gap and is thicker than the thickness of the alignment control protrusion. In the above configuration, the cell gap is defined by the total thickness of the color filter material and the spacer. Therefore, it is not necessary to form the photosensitive resin layer thickly. For this reason, the alignment control protrusion and the spacer can be formed simultaneously.

  As described above, the liquid crystal alignment control protrusion is provided on the inner side of the conductive layer (between the conductive layer and the liquid crystal layer) by the pattern forming method of the present invention so as to be a convex portion on the liquid crystal layer side. Since the orientation of the liquid crystal molecules is regulated to be inclined along the convex surface, a wide viewing angle independent of the position (viewing angle) at which the liquid crystal surface is observed can be secured.

  As described above, the liquid crystal display device using the liquid crystal alignment control protrusion obtained by the pattern forming method of the present invention generally includes a color filter and a color filter side substrate including a conductive layer (electrode) on the color filter. And two substrates (the color filter side substrate and the counter substrate may be provided with a driving element such as a thin film transistor (TFT)) and a counter substrate with a conductive layer (electrode) disposed opposite thereto. The liquid crystal layer is sandwiched by. The liquid crystal alignment control protrusion obtained by the pattern forming method of the present invention is formed using the above-described photosensitive resin composition, and is provided on at least one inner side (particularly with the substrate) of each of the two conductive layers provided on the two substrates. (Between the conductive layers) as a pattern to be convex on the liquid crystal layer side. By providing the liquid crystal alignment control projection of the present invention, the orientation direction of the liquid crystal molecules can be regulated, and a wide viewing angle independent of the observation position (viewing angle) with respect to the liquid crystal surface can be secured.

  Further, as described above, the liquid crystal alignment control protrusion is provided on a liquid crystal display device without a color filter (a device for monochrome display or a field sequential type device that displays while changing the color of the backlight in a short time). It can also be applied.

<Liquid crystal display device>
As described above, the liquid crystal display device of the present invention formed using the patterning substrate obtained by the pattern forming method of the present invention has a liquid crystal display between two substrates each having a conductive layer on the surface facing each other. The layers may be sandwiched and the liquid crystal alignment control protrusions described above may be provided so as to protrude from the outside of the conductive layer on the substrate (between the conductive layer and the liquid crystal layer) toward the liquid crystal layer. Further, an alignment film can be formed on the conductive layer so as to cover them.

  The basic configuration of the liquid crystal display device of the present invention includes: (1) a driving side in which driving elements such as thin film transistors (hereinafter sometimes referred to as “TFTs”) and pixel electrodes (conductive layers) are arranged; A substrate and a color filter side substrate having a color filter and a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion; (2) the color filter The color filter integrated drive substrate directly formed on the drive side substrate and a counter substrate having a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion. And the like.

  Examples of the conductive layer include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; and a metal oxide film such as SiO 2. Is particularly preferred. The drive side substrate, the color filter side substrate, and the counter substrate are made of, for example, a known glass plate such as a soda glass plate, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film. Constructed using.

  As a driving side substrate in which driving elements such as TFTs and pixel electrodes are arranged, for example, TFTs and TFTs connected to data bus lines and gate bus lines arranged in a matrix so as to cross each other vertically are arranged. For example, a conductive layer connected to the data bus line may be provided.

  In any of the above embodiments, a conductive layer is formed on both of the substrates constituting the liquid crystal display element, a voltage is applied between the two conductive layers, and the liquid crystal material sandwiched therebetween changes the alignment state according to the voltage. Display. Accordingly, the structure described above can be formed in any desired shape and form inside any conductive layer (between the conductive layer and the substrate).

  The configuration mode (1) will be described with reference to FIG. As an example of the configuration mode (1), the liquid crystal display device shown in FIG. 19B will be described as an example. One substrate 30 is a color filter side substrate. On the surface of the glass substrate 20 facing the liquid crystal layer 16, a color filter 24, a conductive layer (ITO film) 18 forming a common electrode, and a liquid crystal alignment control protrusion 22 having a trapezoidal cross section formed at an equal pitch. Is formed. Further, an alignment film (not shown) can be provided between the conductive layer 18 and the liquid crystal alignment control protrusion 22 and the liquid crystal layer 16. The other substrate 32 is a drive side substrate including TFTs. On the surface of the substrate 32 facing the liquid crystal layer 16, a TFT (not shown), a conductive layer (ITO film) 14 bonded to the drain electrode of the TFT, and a trapezoidal liquid crystal formed at an equal pitch An alignment control protrusion 22 (only one is shown in FIG. 19) is formed. The substrate 32 is formed with a plurality of gate bus lines that form gate electrodes (not shown), and a plurality of data bus lines (not shown) that are orthogonal to the gate bus lines are formed in parallel. A plurality of TFTs are arranged corresponding to the intersections of the gate bus lines and the data bus lines. Further, an alignment film (not shown) can be provided between the TFT, the conductive layer 14 and the liquid crystal alignment control protrusion 22 and the liquid crystal layer 16. A liquid crystal layer 16 in which a liquid crystal material is sealed is sandwiched between the substrate 30 and the substrate 32, and the liquid crystal alignment control protrusion 22 protrudes from the outside of the conductive layer 18 or 14 to the liquid crystal layer 16 side as a convex portion. The liquid crystal molecules 15 are aligned along the convex surface.

  As described above, the liquid crystal display device of the present invention is provided with the transparent liquid crystal alignment control protrusion without coloration inside the conductive layer of the substrate (between the conductive layer and the liquid crystal layer). A wide viewing angle that does not depend on (viewing angle) can be secured, and the color purity of the three primary colors (B (blue), G (green), R (red)) is not impaired, and there is no hue deviation. A liquid crystal display device capable of displaying a full-color image can be provided.

  The liquid crystal display device shown in FIG. 19A is the same as that shown in FIG. 1B except that it does not include a color filter. That is, the liquid crystal layer 16 formed by encapsulating a liquid crystal material is sandwiched between the substrate 30 and the substrate 32, and the liquid crystal alignment control protrusions 22 protrude from the outer side of the conductive layer 14 to the liquid crystal layer 16 side as protrusions. The liquid crystal molecules 15 are aligned along the convex surface. Also according to this configuration aspect, since the liquid crystal alignment control protrusion is provided between the conductive layer and the liquid crystal layer of the substrate, a wide viewing angle independent of the observation position (viewing angle) with respect to the liquid crystal display surface can be secured. .

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these. Unless otherwise specified, “%” and “part” represent “% by mass” and “part by mass”, and “molecular weight” means “mass average molecular weight”.

-Production of transfer material (1)-
A 75 μm-thick polyethylene terephthalate film (PET film) is prepared as a temporary support, and a thermoplastic resin layer coating liquid H1 having the following composition is applied onto the temporary support and dried to obtain a dry layer thickness of 14 A 6 μm thermoplastic resin layer was formed.

<Composition of coating liquid H1 for thermoplastic resin layer>
・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 80,000, Tg≈70 ° C. ) Methyl ethyl ketone, 1-methoxypropyl-2-acetate solution (FM-601, Mitsui Toatsu Chemical Co., Ltd.) 55.5 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63 / 37,
Methanol, methyl ethyl ketone, 1-methoxypropyl-2-acetate solution (molecular weight = 7000, Tg≈100 ° C.) (Alloset 7055 manufactured by Nippon Shokubai Co., Ltd.)
64.8 parts 1-methoxypropyl-2-acetate solution of a compound obtained by dehydrating and condensing 2 equivalents of pentaethylene glycol monomethacrylate with bisphenol A (manufactured by Shin-Nakamura Chemical Co., Ltd.)
18.1 parts C6F13CH2CH2OCOCH = CH2, H (O (CH3) CHCH2) 7OCOCH = CH2,
Methyl ethyl ketone solution (manufactured by Dainippon Ink & Chemicals, Inc., MegaFuck F-) of a copolymer of H (OCHCH2) 7OCOCH = CH2 (copolymerization molar composition ratio (mass ratio) = 40/55/5, molecular weight = 30,000) 780F) 1.08 parts, methyl ethyl ketone 60.5 parts

Subsequently, an intermediate layer coating solution B1 having the following composition was applied onto the thermoplastic resin layer and dried to form an intermediate layer having a dry layer thickness of 1.6 μm.
<Composition of intermediate layer coating solution B1>
Polyvinyl alcohol (degree of saponification 88%, degree of polymerization 500) (3.22 parts of PVA-205 manufactured by Kuraray Co., Ltd.) Polyvinylpyrrolidone (manufactured by ASP Japan: PVP K-30)
1.49 parts ・ Methanol 42.9 parts ・ Distilled water 52.4 parts

Subsequently, a photosensitive resin layer coating solution T1 having the following composition was prepared, further coated on the intermediate layer, and dried to laminate a photosensitive resin layer having a dry layer thickness of 1.8 μm.
<Composition of Coating Solution T1 for Photosensitive Resin Layer>
-Positive resist solution (FH-2413F manufactured by Fuji Electronics Materials Co., Ltd.,
Novolak resin (14 to 20% by mass) and naphthoquinone diazide ester (4 to 8% by mass) included 53.3 parts, methyl ethyl ketone 46.7 parts, Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.) 0 .04 parts

  Further, an OSM-N film (manufactured by Tredegar Film Products, 23 μm) as a surface protection film is provided on the photosensitive resin layer by pressure bonding, and a thermoplastic resin layer, an intermediate layer, and a photosensitive resin are provided on the temporary support. A transfer material (1) in which a layer and a surface protective film were laminated in this order was produced.

-Production of liquid crystal panels-
First, using a black matrix resin composition K1 shown below on a glass substrate of a predetermined size, a striped dark color separation wall pattern having a line width of 13 μm having an opening of 1.0 μm in height and 130 μm and a frame shape A light shielding part was formed. Thereafter, a colored film composed of R1 (red), G1 (green), and B1 (blue) was formed at a predetermined position by a method for manufacturing a color filter described in JP-A-2000-98599. The composition ratio of R1, G1, and B1 and the coating amount of the pigment are shown below. Further, a transparent electrode film was formed thereon by sputtering of ITO.

<Composition of Resin Composition K1 for Black Matrix>
Black pigment dispersion 1 (13.1% by mass of carbon black, 0.65% by mass of dispersant 1 (the following chemical formula 1), polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, (Molecular weight 37,000) is 6.72% by mass, 1-methoxypropyl-2-acetate is the remainder) 25 parts, 1-methoxypropyl-2-acetate 8.0 parts, methyl ethyl ketone 53 parts, binder 1 (copolymerization composition) Is a random copolymer of benzyl methacrylate / methacrylic acid = 78/22 in molar ratio, molecular weight 38,000 is 27% by mass, 1-methoxypropyl-2-acetate 73% by mass) 9.1 parts hydroquinone monomethyl ether 0 .002 parts DPHA solution (Nippon Kayaku Co., Ltd., trade name KAYA based on dipentaerythritol hexaacrylate) AD DPHA (containing 500 ppm of polymerization inhibitor MEHQ) 76 mass% 1-methoxypropyl-2-acetate 24 mass%) 4.2 parts 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) -3′-bromophenyl] -s-triazine 0.16 parts, Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.044 parts

<Composition and pigment coating amount of resin composition R1 for red colored film>
-R pigment dispersion 1 (8% by mass of CIPR 254, 0.8% by mass of dispersant 1, polymer (ratio of random copolymerization benzyl methacrylate / methacrylic acid = 72/28 molar ratio) 8 mass%, 1-methoxypropyl-2-acetate 83 mass%)
44 parts R pigment dispersion 2: (CIPPR 177 is 18% by mass, polymer (ratio of random copolymerization benzyl methacrylate / methacrylic acid = 72/28 molar ratio) is 12% by mass, 1- 4.9 parts propylene glycol monomethyl ether acetate 7.6 parts methylpropyl ketone 37 parts binder 2 (copolymerization composition is benzyl methacrylate / methacrylic acid / methyl methacrylate = 38 in molar ratio) / 25/37 random copolymer, 27% by weight of molecular weight 38,000, 73% by weight of 1-methoxypropyl-2-acetate) 0.8 parts, DPHA solution 4.4 parts, 2-trichloromethyl- 5- (p-styrylstyryl) -1,3,4-oxadiazole 0.14 parts 2,4-bis (trichloro) Methyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) -3′-bromophenyl] -s-triazine 0.06 parts, phenothiazine 0.010 parts, phosphate ester-based special activator (Tsubakimoto Kasei) (Trade name HIPLAAD ED152)
0.52 parts, MegaFac F-780F (Dainippon Ink Chemical Co., Ltd.) 0.03 parts ○ Pigment coating amount PR-254 0.88 g / m2, PR-177 0.22 g / m2

<Composition of Green Colored Film Resin Composition G1>
G pigment dispersion 1 (CIPGP.36 is 18% by mass, polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 38,000) is 12% by mass. 25.4 parts Y pigment dispersion 1: Trade name CF Yellow EX2585 13.4 parts 1-methoxypropyl- from Gokoku Color Co., Ltd. 2-acetate 23.4 parts methyl ethyl ketone 29.7 parts binder 1 (copolymerization composition is a random copolymer of benzyl methacrylate / methacrylic acid = 78/22 in molar ratio, molecular weight 38,000 is 27% by mass, -Methoxypropyl-2-acetate 73% by mass) 3.2 parts, DPHA solution 4.6 parts, 2-trichloromethyl-5- (p-styrylstyrene) L) -1,3,4-oxadiazole 0.16 parts · 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) -3′-bromophenyl] -S-triazine 0.06 part, phenothiazine 0.005 part, Megafak F-780F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.07 part ○ Coating amount of pigment PG-36 1.12 g / m2, PY -150 0.48 g / m2

<Composition of resin composition B1 for blue colored film>
・ B Pigment Dispersion 1 Trade Name CF Blue EX3357 7.6 parts ・ B Pigment Dispersion 2 Trade Name CF Blue EX3383 13.8 parts ・ 1-Methoxypropyl-2-acetate 24.5 parts ・ Methyl ethyl ketone 31.5 parts ・Binder 3 (Random copolymer having a copolymer composition of benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 in molar ratio, molecular weight of 38,000 is 27% by mass, 1-methoxypropyl-2-acetate is 73% by mass %) 18.4 parts · DPHA solution 4.0 parts · 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole 0.16 parts · phenothiazine 0.02 parts · mega Fax F-780F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.05 part ○ Coating amount of pigment PB-15: 6 0.63 g / m2, P -23 0.07g / m2

  Subsequently, the surface protective film is peeled off from the transfer material (1) obtained above, and the surface of the photosensitive resin layer and the surface of the color filter side substrate on which the ITO film is provided are overlapped to form a laminator (stock) Using Hitachi Industries (Lamic II type), substrate heating temperature (T1) 120 ° C, roll temperature (T2) 120 ° C, substrate transport speed (V) 2.2m / min, laminating pressure 1N / cm After that, only the temporary support of the transfer material was peeled off at the interface with the thermoplastic resin layer and removed.In this state, the photosensitive resin layer, intermediate layer, heat Plastic resin layers are laminated in this order.

-Exposure process-
<Comparative example>
Next, a proximity exposure machine is arranged above the outermost thermoplastic resin layer so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the ultrahigh pressure is passed through the photomask. Proximity exposure was performed with a mercury lamp at an irradiation energy of 150 mJ / cm 2.
In Table 1, it is described as surface exposure.
<Invention>
-Exposure process-
With respect to the photosensitive resin layer and the intermediate layer on the substrate, the following pattern forming apparatus is used in the air atmosphere, and the photosensitive resin layer and the exposure head are moved relative to each other while the wavelength is 405 nm and 80 mJ / cm 2. An image was formed by exposing with an exposure amount.
-Pattern forming device-
The combined laser light source shown in FIGS. 9 to 14 as the light irradiating means, and 768 sets of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction shown in FIG. 16 as the light modulating means are arranged in the sub-scanning direction. The DMD 50 controlled to drive only 1024 × 256 rows of the light modulation means, the microlens array 472 in which the microlenses shown in FIG. 13 are arranged in an array, and the microlens array. A pattern forming apparatus having optical systems 480 and 482 for forming the light on the photosensitive layer was used.
In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed so that only light having passed through the corresponding microlens 55a is incident on each aperture 59a.
In Table 1, it is described as DI exposure.

 Thereafter, for each of the samples exposed in the present invention and the comparative example, a 1% triethanolamine aqueous solution was sprayed onto the substrate at 30 ° C. for 60 seconds with a shower type developing device to dissolve and remove the thermoplastic resin layer and the intermediate layer. . At this stage, the photosensitive resin layer was not substantially developed.

Subsequently, the 2.38% tetramethylammonium hydroxide aqueous solution was developed while sprayed onto a substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions (exposed portions) of the photosensitive resin layer were developed and removed. Then, an alignment control projection pattern made of a photosensitive resin layer patterned into a desired shape was formed on the color filter side substrate.
Subsequently, the color filter side substrate on which the alignment control protrusion pattern was formed was baked at 230 ° C. for 30 minutes, whereby the alignment control protrusion pattern could be formed on the color filter side substrate.

Table 1 shows the results obtained by determining the ratio of missing pixels per 1 cm 2 of the obtained substrate with transparent ribs by the ratio of the number of pixels in which deformation, chipping, missing, etc. are recognized and the number of all pixels.
Using the obtained substrate, a liquid crystal panel was produced by a known method (Japanese Patent Laid-Open No. 11-248921), and the display performance was evaluated.

-Contrast of liquid crystal display device-
For each of the obtained liquid crystal display devices, a ratio (= La: Lb) between luminance La when black is displayed and luminance Lb when white is displayed is obtained, and this ratio is used as a contrast ratio in accordance with the following evaluation criteria. evaluated. The measurement is performed by installing a color luminance meter BM-5 (manufactured by Topcon Corporation) at a distance of 50 cm in the vertical direction of the surface from the surface of the antireflection film attached to the front side to be viewed by the observer. This was done under the assumption of a living environment in a general household.
〔Evaluation criteria〕
A: The contrast ratio was 400: 1 or more.
○: The contrast ratio was 200: 1 or more and less than 400: 1.
Δ: The contrast ratio was 150: 1 or more and less than 200: 1.
X: The contrast ratio was less than 150: 1.
The evaluation results are shown in Table 1.

  From Table 1, all the color filters obtained by the exposure method of the present invention had a contrast ratio of 200: 1 or more and less than 400: 1, and were excellent in contrast as compared with the color filters obtained by surface exposure.

It is a perspective view which shows the external appearance of the exposure unit which concerns on this invention. It is a perspective view which shows the structure of the scanner of the exposure unit which concerns on this invention. (A) is a top view which shows the exposed area | region formed in a photosensitive material, (B) is a figure which shows the arrangement | sequence of the exposure area by each exposure head. 1 is a perspective view showing a schematic configuration of an exposure head according to the present invention. (A) is sectional drawing of the subscanning direction along the optical axis which shows the structure of the exposure head shown in FIG. 4, (B) is a side view of (A). It is the elements on larger scale which show the structure of a digital micromirror device (DMD). (A) And (B) is explanatory drawing for demonstrating operation | movement of DMD. (A) And (B) is a top view which compares and shows the arrangement | positioning of an exposure beam, and a scanning line by the case where it does not arrange | position inclined DMD and the case where it arranges inclined. (A) is a perspective view showing a configuration of a fiber array light source, (B) is a partially enlarged view of (A), and (C) and (D) are plan views showing an arrangement of light emitting points in a laser emitting portion. is there. It is a figure which shows the structure of a multimode optical fiber. It is a top view which shows the structure of a combined laser light source. It is a top view which shows the structure of a laser module. It is a side view which shows the structure of the laser module shown in FIG. It is a partial side view which shows the structure of the laser module shown in FIG. (A) And (B) is sectional drawing which shows the depth of focus in exposure apparatus. (A) And (B) is a figure which shows the example of the use area | region of DMD. (A) is a side view when the use area of DMD is appropriate, (B) is a sectional view in the sub-scanning direction along the optical axis of (A). (A) is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and (B) is projected onto the surface to be exposed when a microlens array or the like is not used. (C) is an example of a plan view showing a light image projected on an exposed surface when a microlens array or the like is used. It is a schematic block diagram which shows one Embodiment of the liquid crystal device of this invention.

10A: Light transmissive substrate 14: Pixel (R, G, B), Color filter 14A: Pixel part (transmission display part)
14B ... Pixel part (reflection display part)
50 ... Digital micromirror device (DMD)
54 ... Lens system 66 ... Fiber array light source 166 ... Exposure head (exposure unit according to the present invention)
171: Pixel unit 172 ... Black matrix

Claims (6)

  Alignment control is performed by applying a photosensitive resin composition for alignment control protrusions on a color filter substrate and performing relative scanning while modulating light based on image data using a two-dimensional spatial light modulation device. A method for producing a color filter, comprising: a step of curing the projection image for use.   The method for applying the photosensitive resin composition for protrusions for orientation control uses a photosensitive transfer material having at least one photosensitive resin layer on a temporary support, and transfers the photosensitive resin layer to a substrate. The method for producing a color filter according to claim 1, comprising:   The method for producing a color filter according to claim 1, wherein the alignment control photosensitive resin composition for protrusions includes a naphthoquinonediazide derivative.   The method for producing a color filter according to any one of claims 1 to 3, wherein the alignment control projection photosensitive resin composition contains a phenol resin.   A color filter formed by the method for producing a color filter according to claim 1.   A liquid crystal display device comprising the color filter according to claim 5.

Images