JP4950453B2 - Color filter, method for manufacturing the same, and liquid crystal display device - Google Patents

Description

  The present invention relates to a manufacturing method of a color filter suitable for a liquid crystal display device (LCD) such as a portable terminal, a portable game machine, a notebook computer, a TV monitor, a PALC (plasma address liquid crystal), a plasma display, and the like, and The present invention relates to a manufactured color filter and a liquid crystal display device using the color filter.

The color filter is an indispensable component for a liquid crystal display (hereinafter also referred to as “LCD” or “liquid crystal display device”). This liquid crystal display is very compact and is equivalent to or better than the conventional CRT display in terms of performance, so it is replacing the CRT display.
The color image of the liquid crystal display is formed by combining the light of the colors that pass through the color filter as they are and are combined with the colors of the pixels constituting the color filter. In general, a color image is formed with pixels of three colors R, G, and B.

  Conventionally, a color filter manufacturing method uses a method in which a photosensitive composition is applied on a glass substrate using a spin coater, dried to form a photosensitive layer, and then the photosensitive layer is exposed and developed. It was. However, recently, since the size of the glass substrate has increased, a spin coater coating method in which the glass substrate has to be rotated has become difficult. In particular, in the case of a large glass substrate having a side exceeding 1.5 m, it is very difficult to apply the photosensitive composition using a conventional spin coater.

Therefore, a slit coater coating method has come to be used as an alternative to the spin coater coating method. Since this slit coater coating method does not need to rotate the glass substrate, it can be applied to a larger glass substrate than the spin coater. Such a slit coater includes a surface plate that holds a substrate (support) horizontally and a coating head that has slit-like nozzles arranged on the surface plate. Then, the application is performed by moving the application head horizontally in a direction (application direction) perpendicular to the slit nozzle while extruding the application liquid from the slit nozzle. According to this slit coater coating method, it is possible to easily cope with a substrate (support) having a size of 1 m ² or more.

  However, the slit coater has a problem that the thickness of the coated photosensitive layer is larger than that of the spin coater, and in particular, the thickness unevenness tends to occur in the direction perpendicular to the coating direction. Here, the thickness variation of the photosensitive layer when scanned in the coating direction is “thickness variation in the coating direction”, and the thickness variation of the photosensitive layer when scanned in the direction perpendicular to the coating direction is “thickness variation in the direction perpendicular to the coating direction”. Called.

  On the other hand, conventionally, as an exposure method of a color filter, a method of exposing through an exposure mask using an ultra-high pressure mercury lamp (batch exposure method) is generally used. For example, Patent Document 1 describes a method of exposing a photosensitive layer formed by a slit coater by a batch exposure method. According to this method, it is possible to form a color filter using a substrate having a large size of 1.8 m × 2 m.

However, when a substrate having a photosensitive layer formed by slit coater coating is exposed by this method, the focal position of the exposure light and the position of the coating layer shift depending on the location, resulting in blurring of the image, and the size of the formed pixel is reduced. There is a problem that it fluctuates.
This is because the tolerance of pixel size has recently become smaller in color filters, and pixel size variation becomes a major problem. In particular, the variation in the pixel size is a serious problem when a black matrix, a spacer, or the like is formed.

Japanese Patent Laid-Open No. 2005-3861

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention has very little line width variation without using a photomask, can be formed with high definition, can reduce the variation in pixel size, has low cost, has excellent display characteristics, and is a portable terminal, portable game, or the like. Manufacturing method of color filter suitably used for liquid crystal display devices (LCD), PALC (plasma addressed liquid crystal), plasma display, etc., color filter manufactured by the manufacturing method of the color filter, and color filter An object is to provide a liquid crystal display device used.

  As a result of intensive studies by the present inventors in order to solve the above problems, the following knowledge has been obtained. That is, when using an exposure method in which light is modulated based on image data using spatial light modulation devices arranged in a two-dimensional direction, and the spatial light modulation device and the substrate are exposed while being relatively scanned, coating is performed by a slit coater method. It has been found that even with the photosensitive layer thus obtained, pixels with smaller pixel size fluctuations can be obtained as compared with the conventional batch exposure method. In this case, if an exposure apparatus having a mechanism (autofocus mechanism) that can automatically adjust the focus when forming an image on the photosensitive layer is used, it is possible to reduce pixel size variation. In particular, it has been found that if the slit coater application direction and the exposure head scanning direction are arranged to be orthogonal to each other, the variation in pixel size can be made extremely small.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A photosensitive layer forming step of forming a photosensitive layer by slit coating a photosensitive composition containing a binder, a polymerizable compound, and a photopolymerization initiator on the surface of the substrate;
The light from the light irradiating means is received and modulated based on the pattern information. The light modulating means modulates the light from the light irradiating means, and the light modulated by the light modulating means The color filter manufacturing method includes at least an exposure step of performing exposure while automatically adjusting a focus when forming an image on an exposed surface of the photosensitive layer through an adjusting unit. In the method for producing a color filter according to <1>, the photosensitive layer formed by applying the slit coater is subjected to maskless digital exposure while performing so-called autofocus, so that the pixel size is smaller than that of the conventional batch exposure method. Pixels with small fluctuations can be efficiently formed, and a high-definition color filter can be manufactured.
<2> The method for producing a color filter according to <1>, wherein the slit coater coating direction and the scanning direction of the exposure head are relatively different.
<3> The method for producing a color filter according to any one of <1> to <2>, wherein the direction of applying the slit coater and the scanning direction of the exposure head are orthogonal to each other.
<4> The light modulated by the light modulation unit is imaged only in a substantially rectangular region including the central part of the imaging unit.
The substantially rectangular exposure area imaged on the exposed surface of the photosensitive layer has an angle formed by the short side direction and the waviness direction of the photosensitive layer, and the long side direction and the waviness direction of the photosensitive layer are The method for producing a color filter according to any one of <1> to <3>, wherein the method is performed so as to be smaller than an angle formed. In the method for producing a color filter according to <4>, the light modulated by the light modulation unit is imaged only in a substantially rectangular region including the central part of the imaging unit. The substantially rectangular exposure region imaged on the exposed surface of the photosensitive layer has an angle formed by the short side direction and the waviness direction of the photosensitive layer, the long side direction and the waviness direction of the photosensitive layer. Therefore, the light selectively irradiated onto an area with good optical performance is imaged, and the focal position is adjusted to an appropriate position. As a result, the photosensitive layer is exposed with high definition.
<5> The <1> to <4, wherein the imaging means forms an image of the light modulated by the light modulation means in a substantially rectangular region whose long side is twice or more the length of the short side. > A method for producing a color filter according to any one of the above.
<6> The focus adjusting unit has a wedge-shaped prism pair formed so that the thickness of the light modulated by the light modulating unit in the optical axis direction changes.
From <1>, the focus is adjusted when the light modulated by the light modulation means is imaged on the exposed surface of the photosensitive layer by moving each wedge-shaped prism constituting the wedge-shaped prism pair. <5> A method for producing a color filter according to any one of the above.
<7> The focus adjusting means includes an optical member constituting the imaging optical system and a piezo element,
Any one of <1> to <6>, wherein the optical member is moved by the piezo element, thereby adjusting a focal point when the light modulated by the light modulation means is imaged on the exposed surface of the photosensitive layer. A method for producing a color filter according to claim 1. In the method for producing a color filter according to <7>, when the optical member is moved by the piezo element, the light modulated by the light modulation unit is imaged on the exposed surface of the photosensitive layer. Since the focus is adjusted, a minute displacement in a direction perpendicular to the focus direction can be suppressed, and the focus position is adjusted with extremely high accuracy while maintaining high beam position accuracy.
<8> The imaging means is either a lens that can rotate around the optical axis with respect to the optical axis of the light modulated by the light modulating means, or a lens that can move in a direction perpendicular to the optical axis. The method for producing a color filter according to any one of <1> to <7>, which is configured.
<9> The method for producing a color filter according to any one of <1> to <8>, wherein the light modulation unit is a spatial light modulation element.
<10> The method for producing a color filter according to any one of <1> to <9>, wherein the light irradiation unit emits laser light emitted from the semiconductor laser element.
<11> The above-mentioned <1>, wherein the light irradiating means is a bundle-shaped fiber light source in which a plurality of optical fibers that enter laser light emitted from a semiconductor laser element from one end and emit incident laser light from the other end are bundled > To <9>. The method for producing a color filter according to any one of <9>.
<12> The method for producing a color filter according to any one of <1> to <11>, wherein the light irradiation unit is capable of combining and irradiating two or more lights.
<13> The light irradiation means collimates the plurality of lasers, the multimode optical fibers, and the laser beams irradiated from the plurality of lasers, and converges them on the incident end face of the multimode optical fibers. It is a manufacturing method of the color filter in any one of said <1> to <12> which has a light source condensing optical system.
<14> The method for producing a color filter according to any one of <1> to <13>, wherein exposure is performed using a light source having an illuminance of 100 mW / cm ² or more.
<15> The method for producing a color filter according to any one of <1> to <14>, wherein the substrate has a size of 500 mm × 500 mm or more.
<16> The method for producing a color filter according to any one of <1> to <15>, wherein the photosensitive composition is colored at least black (K).
<17> Using a photosensitive composition colored in at least three primary colors of red (R), green (G), and blue (B), R, G, and B in a predetermined arrangement on the surface of the substrate. The method for producing a color filter according to any one of <1> to <15>, wherein the color filter is formed by sequentially repeating the photosensitive layer forming step and the exposure step for each of the colors.
<18> At least pigment C.I. I. Pigment Red 254 is colored green (G) with pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 139 and at least a pigment C.I. I. It is a manufacturing method of the color filter as described in said <17> using pigment blue 15: 6.
<19> Pigment C.I. I. Pigment red 254 and pigment C.I. I. Pigment Red 177 at least one pigment is changed to a green (G) coloring pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 150 and at least blue (B) pigment C.I. I. Pigment blue 15: 6 and pigment C.I. I. The method for producing a color filter according to <17>, wherein at least one pigment of pigment violet 23 is used.
<20> A color filter manufactured by the method for manufacturing a color filter according to any one of <1> to <19>.
<21> A liquid crystal display device using the color filter according to <20>.

  According to the present invention, conventional problems can be solved, line width variation is extremely small without using a photomask, high-definition formation is possible, pixel size variation can be reduced, and cost is reduced. Manufacturing method of a color filter excellent in characteristics and suitably used for liquid crystal display devices (LCD) such as portable terminals and portable game machines, PALC (plasma address liquid crystal), plasma display, etc., and manufacturing method of the color filter And a liquid crystal display device using the color filter can be provided.

(Color filter and color filter manufacturing method)
The method for producing a color filter of the present invention includes at least a photosensitive layer forming step and an exposure step, and further includes a development step and other steps appropriately selected as necessary.
The color filter of the present invention is manufactured by the method for manufacturing a color filter of the present invention.
Hereinafter, the details of the color filter of the present invention will be clarified through the description of the method of manufacturing the color filter of the present invention.

[Photosensitive layer forming step]
The photosensitive layer forming step is a step of forming a photosensitive layer by applying a photosensitive coater composition containing a binder, a polymerizable compound, and a photopolymerization initiator to the surface of the base material by slit coater. This is a step of forming other layers.

The method for forming the photosensitive layer and other layers is not particularly limited and may be appropriately selected depending on the purpose. For example, the method for forming by coating, at least pressing and heating each sheet-like layer By performing either, a method of forming by laminating, a combination thereof, and the like can be mentioned.
As the photosensitive layer forming step, at least a photosensitive layer is formed on the surface of the base material by applying the photosensitive composition to the surface of the base material and drying it, and further appropriately selected other layers. The process of forming is mentioned.

  In the photosensitive layer forming step, for example, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition in water or a solvent on the surface of the substrate, and the solution is directly applied. And a method of laminating by drying.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably.

As a method for applying the photosensitive composition solution, slit coater application is used. The slit coater application includes a surface plate that holds the substrate horizontally and an application head that has slit-like nozzles (holes) disposed on the surface plate. The application is performed by moving the application head horizontally in a direction perpendicular to the slit nozzle while extruding the application liquid from the slit nozzle.
Specific examples of the slit coater used for the coating of the slit coater include Japanese Patent Application Laid-Open No. 2004-89851, Japanese Patent Application Laid-Open No. 2004-17043, Japanese Patent Application Laid-Open No. 2003-170098, Japanese Patent Application Laid-Open No. 2003-164787, and Japanese Patent Application Laid-Open No. 2003-164787. No. 2003-10767, JP-A No. 2002-79163, JP-A No. 2001-310147, JP-A No. 2001-310152, JP-A No. 2001-62370, etc., and slit coater device, An apparatus commercially available from Hirano Tech Seed Co., Ltd. or Tokyo Ohka Co., Ltd. is preferably used.
When applying the slit coater, the distance between the tip of the slit nozzle and the glass substrate is kept constant. As a result, a photosensitive layer having a constant coating thickness is formed on the substrate (support).
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

The other layers formed in the photosensitive layer forming step are not particularly limited and may be appropriately selected depending on the intended purpose. For example, an oxygen blocking layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer Etc.
There is no restriction | limiting in particular as a formation method of the said other layer, According to the objective, it can select suitably, For example, the method of apply | coating on the said photosensitive layer, The method of laminating | stacking the other layer formed in the sheet form Etc.

  In addition, as the photosensitive layer forming step, as another aspect, a photosensitive film (hereinafter sometimes referred to as “photosensitive transfer material”) obtained by forming the photosensitive composition into a film shape is formed on the surface of the substrate. By laminating under at least one of heating and pressurization, a step of forming at least a photosensitive layer on the surface of the substrate and further forming other appropriately selected layers may be employed.

In the photosensitive layer forming step, as a method of forming a photosensitive layer on the surface of the base material and other layers appropriately selected as necessary, a support is provided on the surface of the base material and the photosensitive material is formed on the support. A method of laminating a photosensitive film (photosensitive transfer material) having a photosensitive layer formed by laminating a composition and other layers appropriately selected as necessary, while performing at least one of heating and pressing. A photosensitive film obtained by laminating a photosensitive composition on a support is laminated so that the photosensitive composition is on the surface side of the substrate, and then the support is placed on the photosensitive composition. A method of peeling is preferably mentioned.
By peeling the support, it is possible to prevent a blurred image from being formed on the image formed on the photosensitive composition layer due to light scattering, refraction, and the like by the support. can get.
In addition, when the said photosensitive film has a protective film mentioned later, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.

There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, For example, 70-160 degreeC is preferable and 80-130 degreeC is more preferable.
There is no restriction | limiting in particular as said pressurization pressure, According to the objective, it can select suitably, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, a heat press, a heat roll laminator (for example, Hitachi Industries, Ltd.) , Lamic II type), and a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho Co., Ltd.).

  The support is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.

  There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable, 5-175 micrometers is more preferable, and 10-100 micrometers is especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body, According to the objective, it can select suitably, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytri Various plastic films such as fluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  Formation of the photosensitive layer in the photosensitive film can be performed by the same method as the application of the photosensitive composition solution to the substrate and drying (the photosensitive layer forming method of the first aspect).

The protective film is a film having a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-40 micrometers is especially preferable.

  There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, According to the objective, it can select suitably, Usually, it provides on the said photosensitive layer.

  When the protective film is used, the relationship between the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film is preferably adhesive force A> adhesive force B. .

The coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, and more preferably 0.5 to 1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

The protective film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those used for the support, silicone paper, polyethylene, polypropylene laminated paper, polyolefin or polytetrafluoro. An ethylene sheet etc. are mentioned, Among these, a polyethylene film, a polypropylene film, etc. are mentioned as a particularly preferable thing.
Examples of the combination of the support and the protective film (support / protective film) include the combination described in paragraph [0151] of JP-A-2005-70767, polyethylene terephthalate / polyethylene terephthalate, and the like.

  As the protective film, in order to satisfy the above-described relationship of adhesive strength, it is preferable to perform surface treatment to adjust the adhesion between the protective film and the photosensitive layer. For example, as a method of the surface treatment, Examples include the method described in paragraph No. [0151] of JP-A-2005-70767.

  There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a thermoplastic resin layer, an intermediate | middle layer, etc. are mentioned.

-Thermoplastic resin layer-
The thermoplastic resin layer (hereinafter sometimes referred to as a “cushion layer”) enables alkali development, and prevents the transfer target from being contaminated by the thermoplastic resin layer protruding during transfer. In view of the above, it is preferably alkali-soluble, and when transferring the photosensitive transfer material onto the transfer object, a cushion that effectively prevents transfer defects caused by unevenness present on the transfer object It preferably has a function as a material, and is more deformable according to the unevenness present on the transferred body when the photosensitive transfer material is heated and adhered onto the transferred body. preferable.

As a material used for the thermoplastic resin layer, for example, an organic polymer substance described in JP-A-5-72724 is preferable, and the Viker Vicat method (specifically, American Materials Testing Method ASTM D1235) is used. It is particularly preferred that the softening point by the method of measuring the softening point of polymer is selected from organic polymer substances having a temperature of about 80 ° C. or lower. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate or saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymers of the polyamide resin such as N- dimethylamino nylon and the like.
The dry thickness of the thermoplastic resin layer is preferably 2 to 30 μm, more preferably 5 to 20 μm, and particularly preferably 7 to 16 μm.

-Intermediate layer-
The intermediate layer is provided on the photosensitive layer, and is provided between the photosensitive layer and the thermoplastic resin layer when the photosensitive transfer material has a thermoplastic resin layer. In the formation of the photosensitive layer and the thermoplastic resin layer, an organic solvent is used. Therefore, when the intermediate layer is located between them, the layers can be prevented from being mixed with each other.

The intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution.
As the material for the intermediate layer, known materials can be used. For example, polyvinyl ether / maleic anhydride polymer, carboxyalkyl described in JP-A No. 46-2121 and JP-B No. 56-40824 Water-soluble salt of cellulose, water-soluble cellulose ether, water-soluble salt of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, water-soluble polyamide, water-soluble salt of polyacrylic acid, gelatin, ethylene oxide polymer, various Water soluble salts of the group consisting of starch and the like, styrene / maleic acid copolymers, maleate resins, and the like.
These may be used alone or in combination of two or more. Among these, it is preferable to use a hydrophilic polymer, and among these hydrophilic polymers, it is preferable to use at least polyvinyl alcohol, and a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

There is no restriction | limiting in particular as said polyvinyl alcohol, According to the objective, it can select suitably, The saponification rate has preferable 80% or more.
When using the said polyvinyl pyrrolidone, as content, 1-75 volume% is preferable with respect to solid content of this intermediate | middle layer, 1-60 volume% is more preferable, 10-50 volume% is especially preferable.
When the content is less than 1% by volume, sufficient adhesion to the photosensitive layer may not be obtained. On the other hand, when the content exceeds 75% by volume, the oxygen blocking ability may be lowered. .

  The intermediate layer preferably has a low oxygen permeability. When the oxygen permeability of the intermediate layer is large and the oxygen blocking ability is low, it may be necessary to increase the amount of light at the time of exposure to the photosensitive layer, or it may be necessary to lengthen the exposure time, and the resolution also decreases. May end up.

There is no restriction | limiting in particular as thickness of the said intermediate | middle layer, According to the objective, it can select suitably, It is preferable that it is about 0.1-5 micrometers, and 0.5-2 micrometers is more preferable.
If the thickness is less than 0.1 μm, the oxygen permeability may be too high, and if it exceeds 5 μm, it may take a long time for development or removal of the intermediate layer.

  The structure of the photosensitive film is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a thermoplastic resin layer, an intermediate layer, and a photosensitive layer on the support, the temporary support, and the like. The form which has a layer in this order is mentioned. The photosensitive layer may be a single layer or a plurality of layers.

  The photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape. There is no restriction | limiting in particular as the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

  The photosensitive film can be widely used for pattern formation of display members such as color filters, pillar materials, rib materials, spacers, partition walls, etc. Among them, it is suitable for the method for producing a color filter of the present invention. Can be used.

  In addition, there is no restriction | limiting in particular as an exposure method to the laminated body which has the photosensitive layer formed by the photosensitive layer forming method of the said 2nd aspect, According to the objective, it can select suitably, For example, on a support body In the case of a film comprising a photosensitive layer existing through a cushion layer, it is preferable to expose the photosensitive layer through the oxygen-blocking layer after peeling the support, and if necessary, the cushion layer.

<Photosensitive layer>
The photosensitive layer (color resist layer or in-cell structure resist layer) formed in the photosensitive layer forming step includes at least a binder, a polymerizable compound, and a photopolymerization initiator, and is appropriately selected as necessary. And a photosensitive composition containing other components. When producing a color filter, it is preferable to contain a coloring agent.
Examples of the constituent components of the photosensitive layer in the case of constituting a color filter are shown below, but are not limited thereto, and spacers and liquid crystal alignment control protrusions can also be produced.

<< Binder >>
The binder is preferably swellable with an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. From the viewpoints of solubility, suitability for synthesis, ease of preparation of film properties, etc., a vinyl copolymer having a carboxyl group is preferred.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg vinylpyridine, vinyl Pyrrolidone, vinyl carbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, mono (2-acryloyloxyethyl ester) phosphate, phosphoric acid Mono (1-methyl) 2-acryloyloxyethyl ester), functional groups (e.g., a urethane group, a urea group, a sulfonamide group, a phenol group and a vinyl monomer and the like having an imide group).

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butyl acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, specifically, a monomer having an isocyanate group and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

However, in the structural formulas (1) to (3), R ¹ represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

  Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).

However, in the structural formulas (4) to (12), R ¹ represents a hydrogen atom or a methyl group, and n, n1, and n2 represent an integer of 1 or more.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, and acetoxyphenol.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamine (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamine) Emissions, hexafluoroisopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, According to the objective, it can select suitably, For example, 5-50 mol% is preferable, 10-40 mol% Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

The molecular weight of the binder having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the molecular weight is preferably 2,000 to 300,000, and preferably 4,000 to 150,000. More preferred.
When the molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. When two or more binders are used in combination, for example, a combination of two or more binders composed of different copolymerization components, two or more binders having different weight average molecular weights, two or more binders having different degrees of dispersion, etc. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, gelatin and the like.

  Moreover, as the binder, a resin soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 can be used.

There is no restriction | limiting in particular as content of the said binder in the said photosensitive layer, According to the objective, it can select suitably, For example, 5-80 mass% is preferable, 10-70 mass% is more preferable, 15-50 Mass% is particularly preferred.
When the content is less than 5% by mass, the alkali developability may be lowered, and when it exceeds 80% by mass, the stability with respect to the development time may be lowered. The content may be the total content of the binder and the polymer binder used in combination as necessary.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 70 to 250 mgKOH / g is preferable, 90 to 200 mgKOH / g is more preferable, and 100 to 180 mgKOH / g is particularly preferable. preferable.
When the acid value is less than 70 mgKOH / g, the developability may be insufficient or the resolution may be inferior, and the pattern may not be obtained with high definition. At least one of the liquidity and the adhesiveness may deteriorate, and the pattern may not be obtained with high definition.

The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A 51-131706, JP-A 52-94388, JP-A 64-62375, JP-A 2 Examples thereof include epoxy acrylate compounds having acidic groups described in JP-A-97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296776, and the like. Specifically, phenol novolac type epoxy acrylate monotetrahydrophthalate, cresol novolac epoxy acrylate monotetrahydrophthalate, bisphenol A type epoxy acrylate monotetrahydrophthalate, etc. This is obtained by reacting a carboxyl group-containing monomer such as an acid and further adding a dibasic acid anhydride such as phthalic anhydride.
The molecular weight of the epoxy acrylate compound is preferably 1,000 to 200,000, and more preferably 2,000 to 100,000. When the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may deteriorate. If it exceeds 1,000, developability may deteriorate.

An acrylic resin having at least one polymerizable group such as an acidic group and a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as (meth) acrylate group or (meth) acrylamide group, various polymerizations such as carboxylic acid vinyl ester, vinyl ether, allyl ether, etc. Sex double bonds can be used. More specifically, acrylic resins containing carboxyl groups as acidic groups, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexene oxide in the same molecule and (meth) Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an acryloyl group. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. As these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “Cyclomer (CYCLOMER) M- 200; manufactured by Daicel Chemical Industries, Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 And styrene-containing styrene derivatives and acid anhydride copolymers described in JP-A No. 2003-203310 and polyimide precursors described in JP-A No. 11-282155 can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), amide group-containing styrene / acid anhydride copolymer, or polyimide precursor is preferably 3,000 to 500,000, 5,000-100,000 are more preferable. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

  10-60 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said binder, 10-55 mass% is more preferable, and 15-40 mass% is especially preferable. When the solid content is less than 10% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 60% by mass, the exposure sensitivity is increased. May decrease.

<< polymerizable compound >>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

10-60 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 15-50 mass% is more preferable, and 20-40 mass% is especially preferable. If the solid content is less than 10% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 60% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
The ratio between the polymerizable compound and the binder is a mass ratio, preferably polymerizable compound / binder = 0.5 to 1.5, more preferably 0.6 to 1.2, and 0.65 to 1.1. Particularly preferred. If this range is exceeded, problems such as the generation of residues may occur during development, and if it is less than this range, the durability of the completed color filter may be reduced.

<< photopolymerization initiator >>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region. Those having photosensitivity to light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, Examples include thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include compounds described in Wakabayashi et al., Bulletin of the Chemical Society of Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, Compounds described in JP-A-53-133428, compounds described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. Compounds described in the specification, and the like.

  Further, the vicinal polyketaldonyl compound described in US Pat. No. 2,367,660, the acyloin ether compound described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512 Aromatic acyloin compounds substituted with α-hydrocarbons, polynuclear quinone compounds described in US Pat. No. 3,046,127 and US Pat. No. 2,951,758, and JP-A-2002-229194 Organic boron compounds, radical generators, triarylsulfonium salts (for example, salts with hexafluoroantimony and hexafluorophosphate), phosphonium salt compounds (for example, (phenylthiophenyl) diphenylsulfonium salts, etc.) (as cationic polymerization initiators) Valid), International Publication No. 01/7 Such as onium salt compounds described in 428 pamphlet and the like.

  Examples of the compounds described in Wakabayashi et al., Bulletin of the Chemical Society of Japan, 42, 2924 (1969) include 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Tolyl) -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine , 2-n-noni -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Is mentioned.

Examples of the compounds described in the British Patent No. 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4. , 6-Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy) And styryl) -4-amino-6-trichloromethyl-1,3,5-triazine.
Examples of the compound described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compound described in German Patent No. 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -(4-methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloro Methyl) -1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan -2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine and the like can be mentioned.

  F. above. C. Examples of compounds described in Schaefer et al., Journal of Organic Chemistry 29, 1527 (1964) include 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6- Tris (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl)- Examples include 1,3,5-triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compound described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Naphtyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropyl) Phenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloro Chill) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2 , 6-Difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compounds described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl]-. 1,3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4 -Chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine and the like.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1 3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4 -Oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4-oxadiazole Etc.).

  Examples of the oxime derivative include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-one. 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyl And oximino-1-phenylpropan-1-one.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbi (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 , Coumarin compounds described in JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) Acid n-butyl, 4-dimethylaminobenzoic acid phenetic acid 4-dimethylimidobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4- Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl- 4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecyl Amines, aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6- Difluoro 3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428 Gazette, Japanese Patent Publication No.57-1819 No. 57-6096, US Pat. No. 3,615,455, and the like.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  Examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-bisimidazole and 2,2′-bis. (2-Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2, , 6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5.5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis 4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis ( 2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′- Tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′- Bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenyl) Enylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'- Tetrapheni Biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-cyanophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′- Tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trimethylphenyl) ) -4,4 ', 5,5'-tetraphenyl Imidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2 -Phenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-diphenylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferable examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which can cope with laser light having a wavelength of 405 nm in the later-described exposure. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

As content of the said photoinitiator, 0.1-50 mass% is preferable with respect to the total solid component in the said photosensitive composition, 0.5-30 mass% is more preferable, 1-20 mass% Is particularly preferred.
When the content of the photopolymerization initiator is expressed by a mass ratio with the polymerizable compound, the photopolymerization initiator / polymerizable compound is preferably 0.01 to 0.2, more preferably 0.02 to 0.1. Preferably, 0.03 to 0.08 is particularly preferable. If it exceeds this range, there is a problem that a development residue or a precipitation failure occurs. If it is less than this range, sufficient sensitivity may not be obtained.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers according to the purpose. For example, known polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthene (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, , Thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, quinone) Roacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (eg 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl)- 7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- Diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylami Examples include coumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5, 7-dipropoxycoumarin, and others. JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, and the like.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the said photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% Is particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, an organic pigment, an inorganic pigment, dye, etc. are mentioned.
Any one selected from dendritic branched molecules in which metal ions are coordinated as coloring agents, and dendritic branched molecules containing at least one metal particle of metal particles and alloy particles, separately or in combination with these colorants It is also possible to contain other dendritic molecules.

  Examples of the colorant include a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, and a black pigment. When forming a color filter, three primary colors (B, G , R) and black (K), a blue pigment, a green pigment, a red pigment, and a black pigment are preferably used.

  Examples of the pigment include coloring materials described in paragraphs [0038] to [0040] of JP-A-2005-17716, and paragraphs [0068] to [0072] of JP-A-2005-361447. Preferable examples include pigments and colorants described in paragraphs [0080] to [0088] of JP-A-2005-17521.

  In addition, the said colorant, such as an organic pigment, an inorganic pigment, or dye, may be used individually by 1 type, or can also be used in combination of 2 or more type.

In the present invention, in order to effectively realize a good display characteristic (darker color) in both the transmissive mode and the reflective mode in a device such as a portable terminal or a portable game machine, (i) R photosensitive In the composition, pigment C.I. I. Pigment Red 254, and (ii) the pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 139 is used in combination, and in the photosensitive composition of (iii) B, pigment C.I. I. Pigment Blue 15: 6 is preferably used.
Here, the C.I. I. The content of Pigment Red 254 is preferably 0.274 to 0.335 g / m ² when the photosensitive composition is applied with a dry thickness of 1 to 3 μm, and 0.280 to 0.329 g / m ^2. m ² is more preferable, and 0.290 to 0.320 g / m ² is particularly preferable.
C. in said (ii). I. The content of Pigment Green 36 is preferably 0.355 to 0.437 g / m ² when the photosensitive composition is applied at a dry thickness of 1 to 3 μm, and 0.364 to 0.428 g / m ^{2. 2} is more preferable, and 0.376 to 0.412 g / m ² is particularly preferable.
C. in said (ii). I. The content of CI Pigment Yellow 139 is preferably 0.052~0.078g / ^{m 2,} more preferably from 0.060~0.070g / ^{m 2,} 0.062~0.068g / ^{m 2} is particularly preferred. In (ii), C.I. I. Pigment green 36 / C.I. I. The pigment yellow 139 ratio is preferably 5.4 to 6.7, more preferably 5.6 to 6.6, and particularly preferably 5.8 to 6.4.
C. in (iii) above. I. The content of Pigment Blue 15: 6 is preferably 0.28 to 0.38 g / m ² when the photosensitive composition is applied with a dry thickness of 1 to 3 μm, and preferably 0.29 to 0.36 g / m ² is more preferable, and 0.30 to 0.34 g / m ² is particularly preferable.

  In the present invention, in order to achieve high display characteristics (wide color reproduction range and high color temperature) when used in a large-screen liquid crystal display device such as a notebook computer display or a television monitor, I) In the red (R) photosensitive composition, pigment C.I. I. Pigment red 254 and C.I. I. Pigment Red 177 is used, and in the photosensitive composition of (II) green (G), pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 150 is used in combination, and in the photosensitive composition of (III) blue (B), pigment C.I. I. Pigment blue 15: 6 and C.I. I. Pigment violet 23 is preferably used in combination.

Here, the C.I. I. The content of Pigment Red 254 is preferably 0.6 to 1.1 g / m ² when the photosensitive composition is applied with a dry thickness of 1 to 3 μm, and preferably 0.80 to 0.96 g / m. ² is more preferable, and 0.82 to 0.94 g / m ² is particularly preferable.
C. in (I) above. I. The content of Pigment Red 177 is preferably 0.10 to 0.30 g / m ² when the photosensitive composition is applied at a dry thickness of 1 to 3 μm, and preferably 0.20 to 0.24 g / m. ² is more preferable, and 0.21 to 0.23 g / m ² is particularly preferable.
C. in said (II). I. The content of Pigment Green 36 is preferably 0.80 to 1.45 g / m ² and preferably 0.90 to 1.34 g / m ² when the photosensitive composition is applied with a dry thickness of 1 to 3 μm. ² is more preferable, and 0.95 to 1.29 g / m ² is particularly preferable.
C. in said (II). I. The content of pigment yellow 150 is preferably 0.30~0.65g / ^{m 2,} and more preferably 0.38~0.58g / ^{m 2.} In (II), C.I. I. Pigment green 36 / C.I. I. The pigment yellow 150 ratio is preferably 0.40 to 0.50.
C. in said (III). I. The content of Pigment Blue 15: 6 is preferably 0.50 to 0.75 g / m ² when the photosensitive composition is applied with a dry thickness of 1 to 3 μm, and preferably 0.59 to 0.67 g. / more preferably ^m is ^2, and particularly preferably 0.60～0.66G / ^{m 2.}
C. in said (III). I. The content of pigment violet 23, in case of applying a photosensitive composition on a dry thickness of 1 to 3 [mu] m, preferably in a ^{0.03~0.10g / m 2, 0.06~0.08g / m} 2 It is more preferable that it is 0.066-0.074 g / m < ² >. In (III), C.I. I. Pigment Blue 15: 6 / C.I. I. It is preferable that the pigment violet 23 ratio is 12-50.

  The average particle diameter of the pigment is preferably 1 to 200 nm, more preferably 10 to 80 nm, particularly preferably 20 to 70 nm, and most preferably 30 to 60 nm. Since the photosensitive layer is a thin layer, when the particle size of the pigment or the like is not in the above range, it cannot be uniformly dispersed in the resin layer, and it is difficult to produce a high-quality color filter. May be.

As content in the solid content of the said photosensitive composition of the said pigment, if it is at least 30 mass%, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, 30-60 mass% is Preferably, 35-60 mass% is more preferable, and 45-60 mass% is especially preferable.
When the content of the pigment is less than 30% by mass when a high optical density is required, the optical density per unit thickness is insufficient, and the film must be thickened to achieve the desired optical density. If it exceeds 60% by mass, it may be difficult to obtain a difference in solubility between the exposed area and the unexposed area in the developer.

<< Other ingredients >>
In the said photosensitive composition, you may contain components, such as a thermal crosslinking agent, a plasticizer, surfactant, a ultraviolet absorber, a thermal polymerization inhibitor, as another component, for example.

  The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability For example, an epoxy compound having at least two oxirane groups in one molecule, an oxetane compound having at least two oxetanyl groups in one molecule, a melamine resin compound, or the like can be used.

  Examples of the epoxy compound include a bixylenol type or biphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; NISSAN CHEMICAL”). Kogyo Co., Ltd. ”,“ Araldite PT810; manufactured by Ciba Specialty Chemicals ”, etc.), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type Epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type Poxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700 ; Manufactured by Dainippon Ink and Chemicals, Ltd.), epoxy resins having a dicyclopentadiene skeleton (“HP-7200, HP-7200H; manufactured by Dainippon Ink and Chemicals”, etc.), glycidyl methacrylate copolymer epoxy Examples thereof include, but are not limited to, resins (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and the like. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, oxetane groups and novolak resins , Poly (p-hydroxystyrene), cardo-type bisphe And ether compounds with hydroxyl groups, such as siloles, calixarenes, calixresorcinarenes, silsesquioxanes, and the like, as well as unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. And a copolymer thereof.
Examples of the melamine resin compound include alkylated methylol melamine and hexamethylated methylol melamine.

  1-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said epoxy compound or oxetane compound, 3-30 mass% is more preferable. If the solid content is less than 1% by mass, the hygroscopic property of the cured film is increased and the insulation may be deteriorated. If it exceeds 50% by mass, the developability is deteriorated and the exposure sensitivity is decreased. It may occur and is not preferable.

Moreover, in order to accelerate the thermal curing of the epoxy compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Amines, amine compounds such as 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole, 2-ethylimidazole, Imidazo such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole Derivative bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl -2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct S-triazine derivatives such as, etc. can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Bisocyanate such as isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate; the bifunctional isocyanate, trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as preparative and derivatives thereof; and the like.

Furthermore, for the purpose of improving the storage stability of the photosensitive composition of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include isopropanol, tert. Alcohols such as butanol; lactams such as ε-caprolactam, phenol, cresol, p-tert. -Butylphenol, p-sec. -Butylphenol, p-sec. -Phenols such as amylphenol, p-octylphenol, p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime, Active methylene compounds such as cyclohexanone oxime; and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. In place of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethoxymethyl melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

  The addition amount of the thermal crosslinking agent can be added within a range not impairing the effects of the present invention, and the content of the thermal crosslinking agent is 0.01 to 10% by mass of the total solid content of the photosensitive composition. Is preferable, 0.02 to 5 mass% is more preferable, and 0.05 to 3 mass% is particularly preferable.

The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  As content of the said plasticizer, 0.1-50 mass% is preferable with respect to all the components of the said photosensitive layer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the surfactant is appropriately selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like. You can choose.
Further, as the surfactant, the following ^{_{formula, C 8 F 17 SO 2 N}} (R 1) CH 2 CH 2 O (CH 2 CH 2 O n R 2) represented by the suitably fluorine type surfactant Can be mentioned.
In the formula, ^{R 1} and ^{R 2} each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 2 to 30.
Examples of R ¹ include a methyl group, an ethyl group, and an isopropyl group, and examples of R ² include a hydrogen atom.
As said n, 10-25 are preferable and 10-20 are more preferable.
As specific examples of the surfactant represented by the above formula, Megafac F-141 (n = 5), F-142 (n = 10), F = 143 (n = 15), F-144 (n = 20) (Brand name: Dainippon Ink & Chemicals, Inc.).

Furthermore, as said surfactant, surfactant represented by following Formula (1)-(5) is mentioned suitably.
_{Rf1-X- (CH 2 CH 2} O) n R 1 ··· (1)
_{Rf1-X- (CH 2 CH 2} O) n R 2 ··· (2)
_{Rf1-X- (CH 2 CH 2} O) n (CH 2 CH 2 CH 2 O) m R 1 ··· (3)
_{Rf1-X- (CH 2 CH 2} O) n (CH 2 CH 2 CH 2 O) m Rf2 ··· (4)

In the formula (1) ~ (4), R 1 and ^{R 2} are Tansomoto 18, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group include a saturated alkyl group and an unsaturated alkyl group.
Examples of the structure of the alkyl group include those having a linear structure and a branched structure, and among these, those having a branched structure are preferred.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, otatadecyl group , Eicosanyl group, docosanyl group, 2-chloroethyl group, 2-promoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-promopropyl group and the like. In addition, these alkyl groups may be substituted with a halogen atom, an acyl group, an amino group, a cyano group, an alkyl group, an alkoxy group, an aryl group which may be substituted with alkyl or haloalkyl, an amide group, or the like.
In the above formulas (1) to (4), Rf1 and Rf2 each independently represent a perfluoro group having 1 to 18, preferably 2 to 12, and more preferably 4 to 10 carbon atoms.
Examples of the perfluoro group include a saturated perfluoro group and an unsaturated perfluoro group.
Examples of the structure of the perfluoro group include those having a linear structure and a branched structure. Among these, those having a branched structure are preferred, and at least one of Rf1 and Rf2 has a branched structure. A thing is mentioned more suitably.
Examples of the perfluoro group include perfluorononenyl, perfluoromethyl, perfluoropropylene, perfluorononinel, perfluorobenzoic acid, perfluoropropylene, perfluoropropyl, perfluoro (9-methyloctyl), perfluoro Fluoromethyloctyl, perfluorobutyl, perfluoro-3-methylbutyl, perfluorohexyl, perfluorooctyl, perfluoro 7-octylethyl, fluoroheptyl, perfluorodecyl, perfluorobutyl and the like can be mentioned. These perfluoro groups may be substituted with a halogen atom, acyl group, amino group, cyano group, alkyl group, alkoxy group, alkyl or haloalkyl, or may be substituted with an aryl group, an amide group, or the like. Good.
Rf1 and Rf2 may be the same as or different from each other.
In said Formula (1)-(4), n represents the integer of 1-40, Preferably the integer of 4-25 is represented.
In said Formula (1)-(4), m represents the integer of 0-40, Preferably the integer of 0-25 is represented.
In the formula (1) ~ (4), -X- _{is, - (CH 2) l -} (l 1 to 10, preferably represents an integer of 1 to 5), - CO-O -, - O -, -NHCO-, or -NHCOO- is represented.
In the formula (5), R ₃ , R ₄ , and R ₅ represent a hydrogen atom or a methyl group, and a, b, c, p, and q represent arbitrary positive numbers, and are appropriately selected as necessary. Examples include a = 50, b = c = 25, and p = q = 10. r and s represent arbitrary positive integers and are appropriately selected as necessary. Examples thereof include r = 2 and s = 6. C _r H _2r and C _s F _{2s + 1} include both a straight chain structure and a branched structure when r and s are 3 or more. Specific examples of the surfactant represented by the formula (5) include Megafac F-780F (a = 40, b = 5, c = 55, r = 2, s = 6, p = q = 7; Dainippon Ink & Chemicals, Inc.).
The surfactants represented by the formulas (1) to (5) can be used singly or in combination of two or more.

As content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive composition.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  When the photosensitive composition contains the surfactant, the fluidity as a coating liquid is improved, and the adhesion of the liquid in the nozzle, piping, and container of a slit coater used in the coating process is improved. Since the residue remaining as dirt in the nozzle can be effectively reduced, the amount of cleaning liquid required for cleaning at the time of switching the coating liquid and the working time can be reduced, and the productivity of the color filter can be improved. In addition, it is possible to improve surface unevenness that occurs when the color resist layer is formed.

The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, etc. Be
As content of the said thermal-polymerization inhibitor, 0.0001-10 mass% is preferable with respect to all the components of a photosensitive composition, 0.0005-5 mass% is more preferable, 0.001-1 mass% is Particularly preferred.

Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds, etc., in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenyl acrylate, 2,2'-hydroxy-4- Methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethol-4-pyridine) -seba 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4 -Piperenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5 Triazin-2-yl] amino} -3-phenylcoumarin and the like.
In addition, 0.5-15 mass% is preferable, as for content of the ultraviolet absorber with respect to the total solid of a photosensitive composition, 1-12 mass% is more preferable, and 1.2-10 mass% is especially preferable.

The photosensitive composition for forming the photosensitive layer can be prepared using a solvent.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexane, ethyl carbitol acetate, butyl Preferred examples include carbitol acetate and propylene glycol methyl ether acetate. These solvents can be used alone or in combination of two or more.
There is no restriction | limiting in particular as the addition amount of the said solvent at the time of preparation of the said photosensitive composition, According to the objective, it can select suitably, The total solid content concentration of the said photosensitive composition is 5-80 mass%. It is preferable to add so that it may become, it is more preferable to add so that it may become 10-60 mass%, and it is especially preferable to add so that it may become 15-50 mass%.

The thickness of the photosensitive layer is preferably 0.3 to 10 μm, more preferably 0.75 to 6 μm, and particularly preferably 1.0 to 3 μm.
If the thickness of the photosensitive layer is less than 0.3 μm, pinholes are likely to occur when the coating solution for the photosensitive layer is applied, and the manufacturing suitability may be reduced. If the thickness exceeds 10 μm, unexposed areas are removed during development. It may take a long time to do

<Base material>
The substrate used in the photosensitive layer forming step is not particularly limited and may be appropriately selected from known materials having high surface smoothness to those having an uneven surface according to the purpose. In particular, a plate-like substrate (substrate) is preferable. Specifically, a glass plate (for example, soda glass plate, glass plate sputtered with silicon oxide, non-alkali glass plate, quartz glass plate, etc.), synthetic resinous Examples include films, paper, and metal plates.
The size of the substrate can be a large-sized substrate by adopting slit coater coating, and is preferably 500 mm × 500 mm or more, more preferably 1000 mm × 1000 mm or more.

  The substrate can be used by forming a laminate formed by laminating the photosensitive layer on the substrate. That is, by exposing the photosensitive layer of the laminate to the photosensitive layer, the exposed region can be cured, and a pattern can be formed by a development process described later.

[Exposure process]
The exposure step includes forming a photosensitive layer by slit coating a photosensitive composition containing a binder, a polymerizable compound, a photopolymerization initiator, and a colorant on the surface of the substrate; and
The light from the light irradiating means is received and modulated based on the pattern information. The light modulating means modulates the light from the light irradiating means, and the light modulated by the light modulating means A step of performing exposure while automatically focusing (while performing so-called “autofocus”) when forming an image on the exposed surface of the photosensitive layer via an adjusting unit, and the exposure is maskless exposure. It is.

The maskless exposure (also referred to as “maskless pattern exposure”) refers to the exposure head and the photosensitive layer covered while modulating the light from the light irradiation means based on pattern information (also referred to as “image data”). In this exposure method, a two-dimensional pattern (also referred to as “image”) is formed on the exposed surface of the photosensitive layer by performing relative scanning with the exposed surface.
In the exposure method of the present invention, the direction in which the exposure head scans relative to the surface to be exposed is referred to as the “scanning direction of the exposure head”.
In the maskless exposure of the present invention, it is preferable that the scanning direction of the exposure head and the coating direction of the slit coater intersect each other. The intersecting direction is not particularly specified, but it is particularly preferable to arrange the slit coater application direction and the exposure head scanning direction so as to make the pixel size variation very small.
On the other hand, in the conventional exposure method using a mask, a mask formed with a pattern using a material that does not transmit exposure light or a material that transmits exposure light by weakening the exposure light is used as an optical path on the exposed surface of the photosensitive layer. It is the method of arrange | positioning and performing exposure.

  The light source of light emitted from the light irradiation means is not particularly limited and can be appropriately selected according to the purpose. For example, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a copying machine, etc. Fluorescent tubes, LEDs, and laser beams (semiconductor lasers, solid state lasers, liquid lasers, gas lasers), etc., among these, ultra-high pressure mercury lamps and laser beams are preferable, and light on / off control can be performed in a short time, From the viewpoint of easy light interference control, laser light is more preferable.

  There is no restriction | limiting in particular as a wavelength of the said light source, Although it can select suitably according to the objective, For example, as an ultra-high pressure mercury lamp, i line | wire (365 nm) is preferable, As a solid laser, YAG-SHG solid is preferable. A laser (532 nm) and a semiconductor excitation solid-state laser (532 nm, 355 nm, 266 nm) are preferable. As a gas laser, a KrF laser (249 nm) and an ArF laser (193 nm) are preferable. The semiconductor laser is preferably 300 to 500 nm, more preferably 340 to 450 nm, and particularly preferably 405 nm or 410 nm from the viewpoints of shortening the exposure time of the photosensitive composition and easy availability. .

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of resolution in the photosensitive layer, 5/30 μn is preferable as a 1 / e ² value of a Gaussian beam, 7-20 micrometers is more preferable.
The amount of light energy of the laser beam is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of shortening the exposure time and resolution, 1 to 100 mJ / cm ² is preferable, and 5 to 20 mJ / cm ² is more preferable.
The exposure is preferably performed using an apparatus having an exposure unit in which a plurality of laser heads each incorporating a plurality of spatial modulation devices are arranged in the width direction, or an apparatus that scans laser light in the width direction of the substrate.
In this apparatus, it is preferable to carry out exposure while transporting the substrate in the direction in which the laser heads are lined up or in the direction perpendicular to the laser beam scanning direction, or moving the laser head in this direction on a stationary substrate.
Here, a direction in which a plurality of laser heads are arranged or a direction in which laser light is scanned is referred to as a main scanning direction, and a direction perpendicular thereto, that is, a direction in which the substrate and the laser head relatively move is referred to as a sub-scanning direction.
The focus position of the exposure light is preferably adjusted to a position where the line width becomes the smallest when a fine line image is formed on the recording material. This position differs depending on the type of recording material and the substrate and cannot be defined unconditionally, but is often the surface of the photosensitive layer or the central portion in the thickness direction of the photosensitive layer.

The light source is preferably a bundle-shaped fiber light source in which a plurality of optical fibers that enter light from one end and emit the incident light from the other end are bundled, and the optical fiber receives two or more light from the light source. More preferably, the combined laser beam can be emitted.
In this case, the illuminance of the light source is preferably 100 mW / cm ² or more, and more preferably 20 mW / cm ² or more. When the illuminance is less than 10 mW / cm ² , the photosensitive layer is not sufficiently cured, so that the thickness of the pixel portion varies and the display quality of the display may be lowered.
There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of synthesizing and irradiating a combined laser beam with a lens system that collects light and couples it to the multimode optical fiber can be mentioned.

  In the exposure step, the light modulating means for modulating the light from the light irradiating means is a two-dimensional shape of n (where n is a natural number of 2 or more) that receives and emits the light from the light irradiating means. There is no particular limitation as long as it has arranged picture element parts and the picture element parts can be controlled based on pattern information, and can be appropriately selected according to the purpose. For example, a spatial modulation element And an optical polygon mirror (polygon mirror).

The spatial light modulation element is not particularly limited and may be appropriately selected depending on the intended purpose. However, a digital micromirror device (DMD) or a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM) may be used. Preferred examples include a special light modulator, a mirror gradation type spatial modulation element, an optical element that modulates transmitted light by an electro-optic effect (PLZT element), and a liquid crystal light shutter (FLC).
Note that MEMS is a general term for a micro system in which micro-sized sensors, actuators, and control circuits are integrated by micro machining technology using an IC manufacturing process as a substrate. A MEMS type spatial light modulator is an electrostatic force. It means a spatial light modulation element driven by an electromechanical operation using Further, a plurality of Grading Light Valves (GLVs) arranged in two dimensions can be used. In a configuration using these reflective spatial light modulator (GLV) and transmissive spatial light modulator (LCD), a lamp or the like can be used as the light source in addition to the laser.
Among these spatial light modulation elements, DMD and mirror gradation type spatial modulation elements are more preferable, and DMD is particularly preferable.

  The optical polygon mirror (polygon mirror) is a rotating member having a plurality of (for example, six) planar reflecting surfaces, and is not particularly limited as long as light can be scanned by rotation. Can be selected as appropriate. In the exposure using the optical polyhedron (polygon mirror), the exposed surface of the photosensitive layer is moved at a right angle to the scanning direction of the optical polyhedron (polygon mirror), so that the front surface of the exposed surface is moved. Can be exposed.

In the exposure step, the method for exposing the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include digital exposure and analog exposure, but digital exposure is preferred. .
The digital exposure method is not particularly limited and may be appropriately selected depending on the purpose. For example, the digital exposure method is performed using laser light modulated according to a control signal generated based on predetermined pattern information. Is preferred.
Furthermore, in the exposure step, the method for exposing the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of enabling high-speed exposure in a short time, It is preferably carried out while relatively moving the photosensitive layer, and particularly preferably used in combination with the digital micromirror device (DMD).

The exposure step is preferably performed in an inert gas atmosphere. The method for exposing the photosensitive layer formed in the photosensitive layer forming step is not particularly limited and can be appropriately selected according to the purpose. For example, a method of spraying an inert gas directly on the surface of the photosensitive layer, A sample on which a photosensitive layer to be exposed is placed in an exposure space in a sample table in which one side of the frame-shaped frame is opened and an inert gas introduction hole is formed on at least one remaining side. Examples thereof include a method of performing exposure while introducing an inert gas from an active gas introduction hole and covering the surface of the photosensitive layer with an inert gas.
In addition, it is possible to introduce an inert gas into the sealed space under reduced pressure by using the exposure space as a sealed space.
The inert gas is not particularly limited as long as it can prevent the polymerization reaction of the photosensitive layer from being inhibited by the influence of oxygen, and can be appropriately selected according to the purpose. For example, nitrogen, helium, argon, etc. Is mentioned.

<Auto focus>
The autofocus is performed using an exposure apparatus having a known autofocus function.
As such an exposure apparatus with an autofocus function, for example, the defocus amount from the imaging surface at the focus position (position in the optical axis direction of the projection optical system) of a predetermined measurement point in each shot area of the wafer is set. An exposure composed of a focus position detection sensor (hereinafter referred to as “AF sensor”) for detection and a servo system for controlling the height of the Z stage and keeping the defocus amount within an allowable range. And an exposure apparatus provided with a focal position accuracy correction method described below.
Among the “AF sensors”, the oblique incidence type detection device re-images the slit pattern image projected obliquely to a predetermined measurement point in the exposure field by the light receiving unit, and the focus position on the surface of the wafer is determined. When it changes, the position of the re-formed slit pattern image changes, so that the focus position at the measurement point is detected.
For example, as disclosed in Japanese Patent No. 3305448, a mask stage that scans a mask on which a transfer pattern is formed with respect to a variable illumination area having a predetermined shape in a predetermined direction, and photosensitive in synchronization with the mask stage. And a substrate stage that scans the substrate in a predetermined direction, and is provided in a scanning type exposure apparatus that sequentially exposes a mask pattern onto the substrate, and an apparatus for aligning the exposure surface of the substrate with a predetermined reference surface A surface setting means provided on the substrate stage for aligning a predetermined approximate plane of the exposure surface of the substrate with the predetermined reference surface, an exposure area of the mask pattern, and a front side in the scanning direction with respect to the exposure area. A surface position setting device having a height detection means for detecting the height of the exposure surface of the substrate at a plurality of measurement points in a measurement region composed of the side region is also a suitable example.

Hereinafter, an embodiment of a method for producing a color filter of the present invention and an exposure apparatus suitably used for the method for producing the color filter will be described with reference to the drawings.
FIG. 1 shows a schematic external view of an exposure apparatus 10 relating to the exposure process of the pattern forming method of the present invention. The exposure apparatus 10 is a flat plate for adsorbing and holding a sheet-like laminate (hereinafter referred to as “photosensitive material 12”) formed by laminating the photosensitive layer of the pattern forming material on a substrate to be processed. The moving stage 14 is provided. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. Further, the exposure apparatus 10 includes a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is installed at the center of the installation table 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is installed on one side of the gate 22 and a plurality of sensors 26 for detecting the front and rear ends of the photosensitive material 12 are installed on the other side. The scanner 24 and the sensor 26 are respectively fixed to the gate 22 and installed above the moving path of the stage 14. The scanner 24 and the sensor 26 are electrically connected to a controller (not shown), and the operation is controlled by the controller.

  The stage 14 is provided with an exposure surface measurement sensor 28 for detecting the amount of laser light emitted from the scanner 24 to the exposed surface of the photosensitive material 12 when the exposure by the scanner 24 is started. The exposure surface measurement sensor 28 is extended in the direction orthogonal to the stage moving direction at the end of the exposure surface side of the installation surface of the photosensitive material 12 in the stage 14.

FIG. 2 is a schematic external view of the scanner 24.
As shown in FIG. 2, the scanner 24 includes, for example, ten exposure heads 30 arranged in a substantially matrix of 2 rows and 5 columns.
Each exposure head 30 includes a DMD that is a spatial modulation element as the light modulation unit, and projects a two-dimensional pattern formed by the DMD onto the photosensitive material 12.
An exposure area 32 indicates a projection area when a two-dimensional pattern emitted from each exposure head is projected onto the photosensitive material 12. As the stage 14 moves, a strip-shaped exposed region 34 by the exposure head 30 is formed on the photosensitive material 12.

<< Exposure head >>
3 is a conceptual diagram for explaining a schematic configuration of the exposure head 30, and FIG. 7 is a diagram for explaining optical elements constituting the exposure head 30 along the optical path of laser light propagating through the exposure head 30. As shown in FIG. It is.
The exposure head 30 includes a light source unit 60, a DMD irradiation optical system 70, a DMD 80, an imaging optical system 50 as the imaging means, and a wedge-shaped prism pair 54 as the focusing means. Configured.

  As shown in FIG. 4, the light source unit 60 includes a plurality of (for example, 14) LD modules 40, and one end of a first multimode optical fiber 41 is coupled to each LD module 40. A second multimode optical fiber 68 having a smaller cladding diameter than that of the first multimode optical fiber is coupled to the other end of the first multimode optical fiber 41.

  As shown in detail in FIG. 5, seven ends of the second multimode optical fiber 68 opposite to the first multimode optical fiber 41 are arranged along the direction orthogonal to the scanning direction, and they are arranged in two rows. Thus, the laser emitting unit 66 is configured.

  As shown in FIG. 5, the laser emitting portion 66 constituted by the end portion of the second multimode optical fiber 64 is sandwiched and fixed between two support plates 65 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the second multimode optical fiber 64 for protection. The light exit end face of the second multimode optical fiber 68 is likely to collect dust and easily deteriorate due to its high light density, but by arranging the protective plate as described above, it prevents dust from adhering to the end face, Moreover, deterioration can be delayed.

  The LD module 40 is composed of a combined laser light source shown in FIG. The combined laser light source includes a plurality of (for example, seven) semiconductor laser elements LD chips LD1, LD2, LD3, LD4, LD5, LD6, and LD7 arranged and fixed on the heat block 400, and LD chips LD1 to LD1. The collimator lenses 401, 402, 403, 404, 405, 406 and 407 provided corresponding to each of the LDs 7, one condensing lens 90, and one first multimode optical fiber 41 are configured. Yes. The number of semiconductor laser elements is not limited to seven, and other numbers may be adopted. Further, instead of the seven collimator lenses 401 to 407 as described above, a collimator lens array in which these lenses are integrated may be used.

  The LD chips LD1 to LD7 are chip-like lateral multimode or single mode GaN-based semiconductor laser elements, all oscillation wavelengths are common (for example, about 405 [nm]), and maximum outputs are all common (for example, 100 [mW] for a multimode laser and 30 [mW] for a single mode laser. If the wavelength range is 350 [nm] to 450 [nm], semiconductor laser elements having oscillation wavelengths other than the above 405 [nm] may be used as the LD chips LD1 to LD7.

In this way, the laser beams emitted from the plurality of LD chips LD1 to LD7 are incident on one first multimode optical fiber 41 and multiplexed, and further, the amount of light per area is large as a fiber bundle-shaped light source. By using a high brightness light source, the Etendue can be reduced while improving the optical power.
Accordingly, the spatial light modulation by the spatial light modulator only in the region including the central portion of the imaging means can suppress the illumination NA value even if the illumination area for the illuminated object (light modulator) is reduced. it can. Thereby, even when the imaging optical system is disposed on the downstream side of the illumination object, the depth of focus of the imaging optical system can be increased, and the focus deviation of the formed exposure image can be suppressed. The effect is obtained.
A detailed relationship between etendue and depth of focus is described in Japanese Patent Laid-Open No. 2005-018013.

  In the above description, the case where the light emitted from the light irradiation unit is configured by combining the plurality of LD chips LD1 to LD7 has been described. However, the semiconductor laser element and one end of the optical fiber are connected to each other without combining. The optical fiber having a smaller cladding diameter than that of the optical fiber may be coupled to the other end of the optical fiber. In this case, it is preferable to use a multimode high-power laser as the semiconductor laser element, and a high-intensity light source can be realized by using such a high-power laser.

As shown in FIG. 7, the DMD irradiation optical system 70 includes a collimator lens 71, micro fly's eye lenses 72 and 73, a field lens 74, a mirror 75, and a prism 76.
The collimator lens 71 is a lens for making the plurality of laser beams emitted from the laser beam emitting unit 61 into a substantially parallel beam.
The micro fly's eye lenses 72 and 73 are formed by arranging a large number of microlens cells vertically and horizontally, and are lenses for uniformizing the light quantity distribution of the laser light applied to the DMD 80. The laser light that has passed through the micro fly's eye lenses 72 and 73 passes through the field lens 74, is reflected by the mirror 75, and enters the prism 76.
The prism 76 is a TIR prism (total reflection prism) and totally reflects the laser light reflected by the mirror 75 toward the DMD 80. Details of the DMD 80 will be described later.
The DMD irradiation optical system 70 may include a rod integrator as a means for uniformizing the light amount distribution.

-Imaging means-
-Imaging optics-
The image forming optical system 50 is an image forming means for forming an image on the photosensitive material 12 and projecting a two-dimensional pattern formed by modulating the laser light from the light irradiation means by the DMD 80. As shown in FIG. 7, the imaging optical system 50 includes a first projection lens 51, a second projection lens 52, a microlens array 55, and an aperture array 59.
The two-dimensional pattern formed by being reflected by each micromirror that constitutes the DMD 80 is transmitted through the first projection lens 51 and enlarged and imaged by a predetermined magnification (for example, three times). Here, the light beam La transmitted through the first projection lens 51 is individually condensed by each microlens 55 a of the microlens array 55 disposed in the vicinity of the image forming position by the first projection lens 51. The individually condensed light beams pass through the aperture 59a to form an image. The two-dimensional pattern imaged through the microlens array 55 and the aperture array 59 is transmitted through the second projection lens 52 and further magnified to a predetermined magnification (for example, 1.67 times), and the wedge-shaped prism pair 54. And is imaged on the photosensitive material 12. Finally, the two-dimensional pattern formed by the DMD 80 is magnified at a magnification (for example, 3 × 1.67 × = 5 times) obtained by multiplying the magnifications of the first projection lens 51 and the second projection lens 52, respectively. And projected onto the photosensitive material 12.
Note that the imaging optical system 50 is not necessarily provided with the second projection lens 52.

8A and 8B are plan views showing a projection lens 300 that constitutes the first projection lens 51 and the second projection lens 52. FIG.
In order to improve the exposure performance of the exposure apparatus, a projection lens having high lens optical performance (suppression of field curvature, astigmatism, distortion, etc., high telecentricity) is required. However, an attempt to improve lens optical performance over the entire area of the projection lens leads to an increase in the cost of the lens, which makes it difficult to manufacture a large-diameter lens. On the other hand, in recent years, it has been clarified that it is possible to manufacture a projection lens by intentionally distorting a predetermined region in order to improve lens optical performance in an arbitrary region of the projection lens.

  Therefore, for example, by giving distortion to the peripheral portion of the projection lens and reducing the distortion of the central portion, the lens optical performance in the region including the central portion of the projection lens is improved, and further, in the region including the central portion. The two-dimensional pattern formed by the DMD 80 can be transmitted and imaged. Specifically, as shown in FIG. 8A, a region 320 that is a peripheral region of the projection lens 300 is given a characteristic that the field curvature is large, and the region 330 has a large distortion, and the region including the central portion of the projection lens 300 correspondingly. The lens optical performance can be improved by reducing the distortion of the lens.

However, as shown in FIG. 8A, for example, when the two-dimensional pattern formed by the DMD 80 is irradiated and transmitted through the region 310 of the projection lens 300, a part of the two-dimensional pattern has a large curvature of field and distortion. Since the region including the characteristic is transmitted, the two-dimensional pattern needs to be irradiated to the region 340 having good lens optical performance in the projection lens 300.
Therefore, in order to select a region 340 with good lens optical performance of the projection lens 300 and irradiate a two-dimensional pattern, for example, projection is performed in the direction of arrow A shown in FIG. 8B around the optical axis of the light of the two-dimensional pattern. It is preferable to rotate the lens 300. By this rotation, the region 340 with good lens optical performance can coincide with the region 310 irradiated with the two-dimensional pattern, and the two-dimensional pattern can be transmitted through the region 340 with good lens optical performance.
In this way, by forming an image by transmitting a two-dimensional pattern in a region having good lens optical performance, the image quality when the two-dimensional pattern is projected onto the photosensitive material 12 can be improved.

  In addition, when a large-diameter projection lens is used, it is difficult to manufacture if an attempt is made to obtain sufficient lens optical performance in the entire area of the projection lens. By imparting distortion and reducing lens distortion in the region including the central portion, high lens optical performance can be obtained. By using such a large-diameter projection lens, the exposure area can be expanded and the exposure speed can be increased.

  In order to form an image of the light reflected from the DMD 80 in a partial region including the central portion of the projection lens, the two-dimensional pattern formed by the DMD 80 is like a region 310 shown in FIGS. 8A and 8B. It is desirable that the pattern has a substantially rectangular pattern in which the length of the long side is twice or more than the length of the short side. This will be described in detail in the description of DMD described later.

In order to selectively irradiate the two-dimensional pattern on the region 340 with good lens optical performance of the projection lens 300, the imaging optical system 50 is preferably configured to be rotatable about the optical axis of the light of the two-dimensional pattern. .
9 is a schematic side sectional view of the lens barrel 400 including the imaging optical system 50, and the lower diagram in FIG. 9 is a schematic plan view of the lens barrel 400 viewed from the direction of arrow B in the upper diagram in FIG. FIG.
The lens barrel 400 has a flange-like flange 410 on the side surface. A screw through-hole 412 is formed in the flange 410 for each α [°]. A female screw hole (not shown) is also formed in the bracket 420 corresponding to the screw through hole 412 for each α [°], and a screw (not shown) is inserted into the screw through hole 412 of the flange 410 so that the bracket 420 The flange 410 and the bracket 420 are fixed by screwing into the corresponding female screw holes. With this structure, the lens barrel 400 can be fixed at an arbitrary angular position by rotating by α [°] around the optical axes of the first projection lens 51 and the second projection lens 52. Further, when fixing the flange 410 and the bracket 420 with screws, the screws may be inserted into all the screw through holes 412 of the screw through holes 412 and screwed into the corresponding female screw holes of the bracket 420, For example, a screw may be inserted into two screw through holes 412 located on the diagonal line and screwed into corresponding female screw holes of the bracket 420.

  When the lens barrel 400 is rotated, both the first projection lens 51 and the second projection lens 52 are rotated. Then, the flange 410 and the bracket 420 are fixed at the rotational position showing the best exposure performance while measuring the exposure performance such as the focus and image quality (resolution) of the two-dimensional pattern projected on the photosensitive material 12.

  In this way, the first projection lens 51 and the second projection lens 52 are rotated by rotating the lens barrel 400 around the optical axis of the light of the two-dimensional pattern, and the first projection lens 51 and the second projection lens 52 are rotated. In the constituting projection lens, the region with good lens optical performance can be matched with the irradiation region of the two-dimensional pattern formed by the light modulation means.

In addition, you may comprise the projection lens which comprises the 1st projection lens 51 and the 2nd projection lens 52 so that it can rotate independently for every projection lens.
The lens barrel 400 may be configured to be movable in the direction perpendicular to the optical axis of the two-dimensional pattern, and the first projection lens 51 and the second projection lens 52 may be arranged in the direction perpendicular to the optical axis of the two-dimensional pattern. You may comprise so that each projection lens to comprise can be moved independently.

-Light modulation means-
The light modulation means is not particularly limited as long as it can form two-dimensional pattern light based on pattern information (image signal), and can be appropriately selected according to the purpose. , N is a natural number greater than or equal to 1), and those having a picture element portion arranged in a two-dimensional shape. Among these, a spatial light modulator is preferable, and specifically, DMD is preferable.
Hereinafter, the case where DMD is used as the light modulation means will be described.

A schematic perspective view of the DMD 80 is shown in FIG. The DMD 80 is a spatial light modulation unit that spatially modulates light incident from the DMD irradiation optical system 70 based on pattern information (image signal) to form a two-dimensional pattern.
The DMD 80 has micromirrors 81 as pixel parts (pixels) arranged in a number of n (for example, 1024 × 757) two-dimensionally. Further, the DMD 80 is connected to a controller (not shown) having a data processing unit and a mirror drive control unit.
The data processing unit generates a control signal for controlling the driving of each micromirror 81 arranged in the DMD 80 based on the pattern information (image signal).
The mirror drive control unit controls the angle of the reflection surface of each micromirror 81 of the DMD 80 based on the control signal generated by the data processing unit.
The light reflected by the micromirror 81 inclined at a predetermined angle out of the light irradiated on the DMD 81 by the data processing unit and the mirror drive control unit being inclined at a predetermined angle by the reflection surface of the micromirror 81. Becomes a two-dimensional pattern and enters the imaging optical system 50.

  By the way, as described above, the first projection lens 51 and the second projection lens 52 give distortion to the peripheral portions of the projection lenses constituting the first projection lens 51 and the second projection lens 52, and reduce distortion at the center. Thus, the lens optical performance of the region including the central portion of the projection lens is improved, and the two-dimensional pattern is transmitted through the region including the central portion to form an image. In order to image the two-dimensional pattern in a part of the region including the central portion of the projection lens in this way, the two-dimensional pattern formed by the DMD 80 has a long side length like a region 310 shown in FIG. 8B. Is a substantially rectangular pattern that is at least twice as long as the length of the short side. In order to form such a substantially rectangular two-dimensional pattern, a part of the micromirrors 81 of the DMD 80 is driven and controlled so that the length of the side is two times longer than the length of the short side. Is preferably formed.

The substantially rectangular two-dimensional pattern will be described in detail with reference to FIGS. 11A and 11B.
In the DMD 80, for example, a micromirror 81 having 1024 pixels in the main scanning direction at the time of exposure, that is, the row direction, and 756 pixels in the sub-scanning direction at the time of exposure, that is, the column direction, is two-dimensionally arranged. A 1024 × 240 pixel two-dimensional pattern is formed by using some of the micromirrors 81 (for example, 240 pixels) among the 756 pixels arranged in the column direction.
Here, among the micromirrors 81 arranged in the column direction, the number of micromirrors 81 to be used is desirably about 1/2 to 1/5 of the number of micromirrors 81 arranged in the row direction.

Further, for all the micromirrors constituting the DMD 80, a micromirror that occupies the center of the DMD 80 may be used as in the region 80C shown in FIG. 11A. As shown in the region 80T in FIG. You may use the micromirror which occupies the edge part vicinity of.
Furthermore, when a defect occurs in the micromirror being used, the micromirror region to be used may be appropriately changed according to the situation, for example, by using a micromirror region in which no defect has occurred. .

In this way, in the micromirror 81 constituting the DMD 80, by using a part of the micromirrors 81 arranged in the column direction, the length of the long side is substantially rectangular, which is longer than the length of the short side. A two-dimensional pattern can be formed, and it becomes easy to irradiate only the region having high lens optical performance of the projection lens constituting the first projection lens 51 and the second projection lens 52.
In addition, since the data processing speed of the DMD 80 is proportional to the number of micromirrors 81 to be controlled (number of pixels), the data processing speed can be reduced by using some of the micromirrors 81 arranged in the column direction. The exposure speed can be increased.
Further, by reducing the two-dimensional pattern formed by the DMD 80, the microlens array 55 in which the microlenses corresponding to the micromirrors 81 are arranged in an array can be reduced in size. Since the microlens array is an expensive optical member, the cost of the exposure apparatus can be reduced.

  Note that, in order to form a substantially rectangular two-dimensional pattern in which the length of the long side is longer than the length of the short side, a part of the micromirrors 81 arranged in the column direction in the DMD 80 is used. However, a DMD in which the number of micromirrors in the long side direction is twice or more than the number of micromirrors in the short side direction may be used in advance.

-Focus adjustment means-
--Wedge type prism pair--
FIG. 12 is a side view showing the configuration of the wedge-shaped prism pair 54, and FIG. 13 is a schematic perspective view showing the wedge-shaped prism pair 54.
The wedge-shaped prism pair 54 is a focus adjusting means for adjusting the focal point when the two-dimensional pattern is imaged by changing the optical path length of the light of the two-dimensional pattern.
The wedge prism pair 54 includes wedge prisms 540A and 540B, base prism holders 541A and 541B for fixing the wedge prisms 540A and 540B, and a slide base 542A and a slide base disposed at both ends of the base prism holder 541A. The slide unit 545 includes a slider 542B that moves on the surface 542A, and a drive unit 546 that moves the slide unit 545. For the wedge-shaped prism pair 54, as shown in FIG. 13, for example, a parallel plate made of a transparent material such as glass or acrylic is cut along a plane Hk inclined obliquely with respect to the parallel planes H11 and H22 of the parallel plate. A pair of wedge prisms A and B obtained by doing so can be used as the wedge prisms 540A and 540B.

  The wedge-shaped prisms 540A and 540B shown in FIG. 12 are fixed to the base prism holders 541A and 541B via an air layer 550 having a width t (for example, 10 [um]). In addition, linear sliding is possible by a combination of the slide base 542A and the slider 542B, and the drive unit 546 moves the positions of the wedge prisms 540A and 540B to each other so that the width t of the air layer 550 does not change. Move relatively in the direction (direction of arrow u in the figure). By the movement of the slide portion 545, the thickness of the wedge-shaped prism pair 54 in the optical axis direction (the thickness obtained by removing the width t of the air layer 550 from the thickness of the plane parallel plate) is changed. That is, the optical path length of the light forming the two-dimensional pattern is changed by the wedge-shaped prism pair 54.

As described above, by arranging the wedge-shaped prism pair 54 between the second projection lens 52 and the photosensitive material 12, the optical path length of the light of the two-dimensional pattern can be easily adjusted.
Therefore, as compared with the prior art, the focus adjustment when the two-dimensional pattern imaged by the second projection lens 52 is imaged on the photosensitive material 12 can be performed easily and in a short time.

  As shown in FIG. 14, the wedge-shaped prism pair 54 is disposed between the microlens array 55 and the second projection lens 52, thereby changing the optical path length of the light of the two-dimensional pattern. The focus of the pattern may be adjusted.

  Although the case where the wedge-shaped prism pair 54 is used as the focus adjusting means has been described, the focus adjusting means is not limited to this, and the position of the projection lens constituting the imaging optical system 50 is not changed. Any focus adjustment means with high beam position accuracy for performing focus adjustment may be used.

--Focus adjustment means using optical member and piezo element constituting imaging optical system--
As the focus adjusting means, for example, as shown in FIGS. 15A, 15B, 16A, and 16B, a microlens array 55 that is an optical member constituting an imaging optical system is focused using a piezo element 600. Focus adjustment may be performed by moving in the direction (the direction of arrow X in the figure).
By using the piezo element 600, it is possible to perform minute movement in the focus direction while suppressing displacement in the direction perpendicular to the focus direction of the microlens array 55, so that focus adjustment is performed while maintaining stable beam position accuracy. It can be carried out.

<Exposure method>
An exposure method using the above-described exposure apparatus 10 will be described.
FIG. 17A is a perspective view schematically showing the positional relationship between the photosensitive material 12 and the DMD 80. As shown in FIG. 2, the exposure apparatus 10 has been described as including 10 exposure heads 30 having DMDs 80. However, in FIG. 17A and FIG. To do.

As shown in FIG. 17A, when the micromirror 81 occupying the region 80T is used for all the micromirrors 81 of the DMD 80, the photosensitive material 12 is placed with the short side direction of the region 80T facing the waviness direction of the photosensitive material 12. It is preferable to expose the photosensitive material 12 while moving it in the waviness direction (with the short side direction of the region 80T directed to the moving direction of the photosensitive material 12). That is, the exposure is performed so that the substantially rectangular exposure area formed by the area 80T and imaged on the exposed surface of the photosensitive material is substantially parallel to the short side direction and the waviness direction of the photosensitive layer. Preferably it is done.
In FIG. 17A, an exposure area 81 is an exposure area when a two-dimensional pattern is formed using all the micromirrors 81 of the DMD 80, and the exposure area 81T is 2 using the micromirror 81 that occupies the region 80T in the DMD81. This is an exposure area when a dimensional pattern is formed.

FIG. 17B is an enlarged side view showing a portion surrounded by a broken-line frame P in FIG. 17A. As shown in FIG. 17B, when a two-dimensional pattern is formed using all the micromirrors 81 of the DMD 80, the maximum depth difference with respect to the photosensitive material 12 in the exposure area 81 (the maximum of the surface of the photosensitive material 12 in the exposure area 81). The difference in height is d2.
On the other hand, when the micromirror 81 occupying the region 80T is used in the DMD 80, the maximum depth difference with respect to the photosensitive material 12 in the exposure area 81T is d1.
As shown in FIG. 17B, d1 <d2, and the smaller the depth difference, the smaller the degree of undulation of the photosensitive material 12 in the two-dimensional pattern than when the depth difference is large. Therefore, the focal position of the two-dimensional pattern can be adjusted to a more appropriate position.

  Further, when the exposure of one frame is completed and the photosensitive material 12 is moved by moving the stage 14 in the scanning direction, the position of the exposure area 81T is changed, and the degree of undulation of the photosensitive material 12 in the exposure area 81T is changed. Therefore, although the focal position also changes, the focal position is adjusted immediately by the focus adjustment by the wedge prism pair 54. Therefore, exposure having a long focal depth corresponding to the undulation of the photosensitive material 12 can be performed.

Thus, in the micromirrors 81 constituting the DMD 80, when a part of the micromirrors 81 arranged in the column direction is used to form a substantially rectangular two-dimensional pattern, the two-dimensional pattern By performing exposure with the short side direction facing the waviness direction of the photosensitive material 12, the degree of waviness of the photosensitive material 12 in the exposure area 81T can be reduced.
For this reason, the focal position of the two-dimensional pattern can be adjusted to an appropriate position, and the focal depth of the exposure apparatus 10 can be apparently increased as compared with the conventional exposure apparatus. As a result, the exposure image quality can be improved. High-definition pattern exposure is performed.

As shown in FIG. 2, the exposure head 30 is actually attached to the scanner 24 so that the pixel row direction of the DMD 80 forms a predetermined set inclination angle with the scanning direction. Therefore, the exposure area 32 (corresponding to the exposure area 81T in FIGS. 17A and 17B) by each exposure head 30 is a rectangular area inclined with respect to the scanning direction.
In order to minimize the degree of influence due to the waviness of the photosensitive material 12 in the exposure area 81T, it is ideal that the short side direction of the exposure area 81T and the waviness direction of the photosensitive material 12 are perfectly matched. Even if the area 81T has the predetermined set inclination angle, if the short side direction of the exposure area 81T is directed to the waviness direction of the photosensitive material 12 from the long side direction, that is, on the exposed surface of the photosensitive material. The angle formed by the short side direction and the waviness direction of the photosensitive layer in the substantially rectangular exposure region to be imaged is smaller than the angle formed by the long side direction and the waviness direction of the photosensitive layer. It only has to be suitable.

  As described above, the exposure in the pattern forming method of the present invention imparts distortion to the peripheral area of the projection lens constituting the imaging means, and reduces the distortion of the area including the central part, thereby reducing the central part. By using an exposure apparatus equipped with an imaging means that improves the optical performance of the included area, the spatially light-modulated light is imaged by imaging the spatially light-modulated light in the area with good optical performance. The image quality when projected on the material can be improved.

  Also, by giving lens distortion to any area such as the peripheral area of the projection lens and reducing the lens distortion in the area including the central part, even a large aperture projection lens can have high lens optical performance. This increases the exposure area and increases the exposure speed.

  The image forming means in the exposure apparatus can rotate around the optical axis of the spatial light modulated exposure light, or can move in the direction perpendicular to the optical axis, thereby forming a projection constituting the image forming means. The region with good optical performance of the lens is selectively irradiated with light subjected to spatial light modulation.

  Further, by using only a region having a good lens performance including the central portion by giving lens distortion to the peripheral region or the like of the projection lens, the optical system of the focus adjusting means can be used as compared with the case where the entire region of the projection lens is used. As a result, high-definition exposure is performed by an exposure apparatus that realizes a highly accurate stable holding and moving mechanism. Further, the focal position is adjusted with high accuracy while keeping the optical position of the spatially modulated exposure light stable.

  In addition, when concentrating spatially light-modulated light on a small spot through the microlens array, the expensive microlens array can be reduced in size, so that a microlens array with higher pitch accuracy and lower cost can be employed. . Furthermore, by using a piezo element as the focus adjustment means, it is possible to suppress a minute displacement in a direction perpendicular to the focus direction, and to adjust the focus position with high accuracy while maintaining high beam position accuracy.

  Also, each laser beam emitted from a plurality of semiconductor laser elements is incident on one optical fiber and combined, and a high-intensity light irradiation means with a large light amount per area is used as a fiber bundle-shaped light source. Thus, the Etendue can be reduced while improving the optical power, and the numerical aperture (NA) on the DMD side can be reduced. Thus, the numerical aperture on the DMD side can be reduced even when spatial light modulation is performed by the spatial light modulation means only in a substantially rectangular area including the central portion of the imaging means, and the imaging optical system Even when is disposed downstream of the illumination object, the depth of focus of the imaging optical system can be increased, and the focus deviation of the imaged exposure image is suppressed.

  Further, when the imaging means forms an image of the exposure light that has been spatially light-modulated in a substantially rectangular region whose long side is twice or more the length of the short side and projects it onto the photosensitive material, The angle between the short side direction and the waviness direction of the photosensitive layer of the substantially rectangular exposure region imaged on the exposed surface of the photosensitive material is the long side direction and the waviness direction of the photosensitive layer. By performing exposure so that the angle is smaller than the angle formed, the degree of swell of the photosensitive material in the projection area of the projected spatial light modulated exposure light can be reduced, and the focus of the spatial light modulated light is reduced. The position can be adjusted. Thereby, the depth of focus can be apparently increased as compared with the conventional exposure apparatus, and the resolution (exposure image quality) can be improved.

[Development process]
The developing step includes a step of developing the photosensitive layer by exposing the photosensitive layer by the exposing step and removing an unexposed portion.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass sodium carbonate aqueous solution or a potassium carbonate aqueous solution, and a 0.01 to 0.1% by mass potassium hydroxide aqueous solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

The development method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paddle development, shower development, shower & spin development, and dip development.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive layer by shower. Prior to development, it is preferable to spray an alkaline solution having a low solubility of the photosensitive layer with a shower or the like to remove the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the processes in a well-known color filter manufacturing method is mentioned, For example, a hardening process process etc. are mentioned. These may be used alone or in combination of two or more.

-Curing process-
It is preferable to provide a curing treatment step for performing a curing treatment on the photosensitive layer after the development step.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the pattern is formed after the developing step. By the entire surface exposure, curing of the resin in the photosensitive composition forming the photosensitive layer is accelerated, and the surface of the formed pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the pattern is formed after the developing step. The whole surface heating increases the film strength of the surface of the pattern.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

  The color filter manufacturing method of the present invention can form a pattern with high definition and efficiency by suppressing distortion of an image formed on the exposed surface of the photosensitive layer. It can be suitably used for forming various required patterns, and can be particularly suitably used for forming a high-definition color filter pattern.

In the method for producing a color filter of the present invention, as described above, RGB pixels composed of at least three primary colors are formed in a mosaic shape or a stripe shape on a transparent substrate such as a glass substrate by the pattern forming method of the present invention. Can be arranged.
There is no restriction | limiting in particular as a dimension of each pixel, According to the objective, it can select suitably, For example, it is preferable to set it as 40-200 micrometers. In the case of a stripe shape, a width of 40 to 200 μm is usually used.
As the method for producing the color filter, for example, a black matrix is formed on a transparent substrate by performing exposure and development to form a black matrix, and then any one of RGB composed of at least three primary colors. In the predetermined arrangement with respect to the black matrix, exposure and development are sequentially repeated for each color using the photosensitive layer colored in the above, and RGB pixels composed of at least three primary colors are formed on the transparent substrate. The method of forming the color filter arrange | positioned at mosaic shape or stripe shape is mentioned.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises a liquid crystal sealed between a pair of substrates arranged opposite to each other, has the color filter of the present invention, and further has other members as necessary. It becomes.
The color filter of the present invention is intended to be formed on the counter substrate of the liquid crystal display device (the substrate on the side where there is no active element such as a TFT). A BOA method for forming the layer or an HA method having a high aperture structure on the TFT substrate can also be used.

  An overcoat film or a transparent conductive film can be further formed on the color filter as necessary. Thereafter, liquid crystal is sealed between the color filter and the counter substrate, and a liquid crystal display device is manufactured. The liquid crystal display method is not particularly limited and is appropriately selected according to the purpose. For example, ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), OCB (Optically Compensatory Bend), VA (Vertically Aligned), HAN (Hybrid Aligned Nematic), STN (Supper Twisted Nematic), IPS (In-Plane Switching), GH (Guest Host), FLC (ferroelectric liquid crystal), AFLC (antiferroelectric liquid crystal), PDLC (polymer dispersion) Applicable to display methods such as liquid crystal display).

  By using the color filter of the present invention, the liquid crystal display device of the present invention can display a clear color in any of the reflection mode and the semi-transmission mode. It can be suitably used for devices such as portable game machines.

  Examples of the reflective liquid crystal display device include: (1) a driving side substrate in which driving elements such as thin film transistors (hereinafter referred to as “TFTs”) and pixel electrodes (conductive layers) are arranged; A device constructed by placing a color filter side substrate provided with an electrode (conductive layer) opposite to each other with a spacer interposed therebetween and enclosing a liquid crystal material in the gap, and (2) a color filter formed directly on the drive side substrate The color filter integrated drive substrate and the counter substrate provided with the 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 (Japanese Patent Application Laid-Open No. 2003-2003). 241178) and the like.

Examples of the transflective liquid crystal display device include the following devices.
(1) The reflective film has a multilayer structure composed of an adhesive layer and a silver-based thin film, and is disposed on the substrate so as to form an electrically connected pattern via the adhesive layer. An apparatus having an opening for transmitting light in a part of a portion facing a pixel of a filter (see Japanese Patent Application Laid-Open No. 11-52366).
(2) In the light transmission region in one pixel, the colored pixels in the pixel form a colored layer of the same color and the same thickness in the entire region, and the colored layer and the missing colored layer are missing in the light reflecting region. The apparatus which formed the part (refer Unexamined-Japanese-Patent No. 2002-169148).
(3) A uniform concave portion is formed in a light transmission region in one pixel, and a colored layer forming material is used on a glass substrate on which a patterned concave portion is formed in the light reflection region, and the light transmission region Is a device in which a uniform thick colored layer is provided and a patterned colored layer of a thick colored layer portion and a thin colored layer portion is provided in the light reflection region (see Japanese Patent Application Laid-Open No. 2002-258028).
(4) In a color filter that performs color display with three additive primary colors (R, G, B), each pixel of R, G, B is a complementary color of cyan, magenta, and yellow. Specifically, the red pixel is composed of magenta and yellow, the green pixel is composed of cyan and yellow, and the blue pixel is composed of cyan and magenta. In addition, R, G, and B transmissive color display is performed by mixing colors by subtracting two colors, and the two-color pixels are each formed in a single layer in the light reflection region, and R by mixing colors by adding two colors. , G, B reflective color display device (see Japanese Patent Application Laid-Open No. 2002-258029).
(5) An apparatus having a light transmission region and a reflection region in each pixel, and the reflection region has light diffraction and light scattering functions (see Japanese Patent Application Laid-Open No. 2002-268055).
(6) A colored layer in which colored pixels are formed using the same photosensitive colored resin composition, and a colored layer (colored layer) having a thickness for a transmission type in a light transmission region in one pixel. 1) and an apparatus in which a reflective colored layer (colored layer 2) having a thickness smaller than that of the colored layer (colored layer 1) is formed in the light reflecting region (see JP 2002-365422 A). ).
In addition, it is also possible to form colored pixels of the same color in the reflective region and the transmissive region using different materials.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”, respectively.

( Reference Example 1)
An MVA mode liquid crystal display device was manufactured as follows.
<Production of color filter>
-Preparation of colored photosensitive resin composition K1-
The colored photosensitive resin composition K1 is obtained by weighing K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1 and mixing at a temperature of 24 ° C. (± 2 ° C.) for 10 minutes at 150 rpm. Stir. Subsequently, methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) -3'-bromophenyl] -s- Triazine and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) and 150 rpm for 30 minutes. Thus, a colored photosensitive resin composition K1 was prepared.
In addition, the unit of the addition amount of each component in Table 1 is a mass part.

Details of each composition in the colored photosensitive resin composition K1 are as follows.
* Composition of K Pigment Dispersion 1 Carbon black: 13.1 parts (Special Black 250, manufactured by Degussa)
5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenzimidazolone ... 0.65 part Polymer [Random copolymer of benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) (molecular weight 37,000)] ... 6.72 parts ・ Propylene glycol monomethyl ether acetate ... 79.53 parts

* Composition of binder 1-Polymer [Random copolymer of benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]) (molecular weight 40,000)] ... 27 parts-Propylene glycol monomethyl ether acetate 73 Part * Composition of DPHA solution-Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) ... 76 parts-Propylene glycol monomethyl ether acetate ... 24 parts * Surfactant 1: Megafax F-780-F (Dainippon Ink Chemical Co., Ltd.)

-Preparation of colored photosensitive resin composition R1-
The colored photosensitive resin composition R1 shown in Table 1 is obtained by weighing R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate and mixing them at a temperature of 24 ° C. (± 2 ° C.) to 150 r. Stir at pm for 10 minutes. Subsequently, methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4′- (N, N-diethoxycarbonylmethyl) -3′-bromophenyl] -s-triazine and phenothiazine are weighed out and added in this order at a temperature of 24 ° C. (± 2 ° C.), and 10 at 150 rpm. Stir for minutes. Next, Surfactant 1 was weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 30 minutes, and filtered through nylon mesh # 200. Thus, a colored photosensitive resin composition R1 was prepared.

Details of each composition in the colored photosensitive resin composition R1 are as follows. The compositions of the DPHA liquid and the surfactant 1 are the same as those of the colored photosensitive resin composition K1.
* Composition of R pigment dispersion 1-C.I. I. Pigment red 254... 8.0 parts ・ 5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenz Imidazolone ・ ・ ・ 0.8 part ・ Polymer [Random copolymer of benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) (weight average molecular weight 37,000)] ・ ・ ・ 8.0 part ・ Propylene Glycol monomethyl ether acetate ... 83.2 parts

* Composition of R pigment dispersion 2-C.I. I. Pigment Red 177 ... 18 parts Polymer (Random copolymer of benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) (molecular weight 37,000)] ... 12 partsPropylene glycol monomethyl ether acetate・ ・ ・ 70 parts * Binder 2 composition ・ Random copolymer (molecular weight 30,000) of benzyl methacrylate / methacrylic acid / methyl methacrylate (= 38/25/37 [molar ratio]) ・ ・ ・ 27 parts ・ Propylene glycol Monomethyl ether acetate 73 parts

-Preparation of colored photosensitive resin composition G1-
The colored photosensitive resin composition G1 shown in Table 1 is obtained by weighing out the G pigment dispersion 1, the Y pigment dispersion 1, and propylene glycol monomethyl ether acetate and mixing the mixture at a temperature of 24 ° C. (± 2 ° C.) to 150 r. Stir at pm for 10 minutes. Subsequently, methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) -3'-bromophenyl] -s-triazine and phenothiazine are weighed out and added in this order at a temperature of 24 ° C. (± 2 ° C.) and 150 rpm. The surfactant 1 was weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200. Thus, a colored photosensitive resin composition G1 was prepared.

Details of each composition in the colored photosensitive resin composition G1 are as follows. In addition, the composition of the binder 1, the DPHA liquid, and the surfactant 1 is the same as that of the colored photosensitive resin composition K1.
* Composition of G pigment dispersion 1-C.I. I. Pigment Green 36 ... 18 parts Polymer [Random copolymer of benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) (weight average molecular weight 37,000)] ... 12 parts Cyclohexanone 35 parts Propylene glycol monomethyl ether acetate 35 parts * Y pigment dispersion 1
Product name: CF Yellow EX3393 (manufactured by Gokoku Color Co., Ltd.)

<Preparation of colored photosensitive resin composition B1>
The colored photosensitive resin composition B1 shown in Table 1 is obtained by weighing out the B pigment dispersion 1, the B pigment dispersion 2, and propylene glycol monomethyl ether acetate and mixing them at a temperature of 24 ° C. (± 2 ° C.) to 150 r. Stir at pm for 10 minutes. Next, methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and phenothiazine are weighed out, and this temperature is 25 ° C. (± 2 ° C.). Then, the mixture was stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.), and the surfactant 1 was weighed out and added at a temperature of 24 ° C. (± 2 ° C.) for 30 rpm. Stir for 5 minutes at pm and filter through nylon mesh # 200. Thus, a colored photosensitive resin composition B1 was prepared.

Details of each composition in the colored photosensitive resin composition B1 are as follows. In addition, the composition of DPHA liquid and surfactant 1 is the same as that of the colored photosensitive resin composition K1.
* B Pigment dispersion 1
Product name: CF Blue EX3357 (manufactured by Gokoku Dye)
* B Pigment dispersion 2
Product name: CF Blue EX3383 (manufactured by Gokoku Dye)
* Composition of binder 3-Random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate (= 36/22/42 [molar ratio]) (molecular weight 30,000) ... 27 parts-Propylene glycol monomethyl ether acetate-・ 73 parts

(1) Formation of a black (K) image A non-alkali glass substrate having a length of 150 cm, a width of 150 cm, and a thickness of 0.7 mm has nylon hair while spraying a glass detergent solution adjusted to 25 ° C. by a shower for 20 seconds. Washed with a rotating brush, washed with pure water, and then washed with a silane coupling solution (N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.3% aqueous solution; trade name: KBM603, Shin-Etsu Chemical Co., Ltd.) Was sprayed for 20 seconds and washed with pure water. After cleaning, the glass substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device. After cooling the substrate and adjusting the temperature to 23 ° C., a coating rate for glass substrate having a slit-like nozzle (manufactured by FS Japan Co., Ltd., trade name: MH-1600) is applied at a coating speed of 2 m / min. The above colored photosensitive resin composition K1 was applied. Subsequently, after part of the solvent was dried by VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the substrate was surrounded by EBR (edge bead remover). Unnecessary coating solution was removed and prebaked at 100 ° C. for 3 minutes to form a photosensitive layer K1 having a thickness of 4.2 μm.

-Exposure-
The obtained substrate with the photosensitive layer K1 was exposed using the following exposure apparatus with an autofocus function. The beam diameter of the laser beam was 10 μm with a 1 / e ² diameter, and the illuminance was 1000 mW / cm ² . The direction of exposure was such that the direction of application coincided with the scanning direction of the exposure head (shown as 0 degrees in Table 3). By exposure, a grid-like image having a length and width of 200 μm and a line width of 50 μm was formed.

<< Exposure equipment >>
An exposure apparatus 10 whose outline of the appearance is shown in FIG. 1 was used. The configuration of the exposure head of the exposure apparatus is as shown in FIG. 7. Specifically, the combined laser light source shown in FIGS. 4 to 6 as the light irradiation means and the light modulation means as shown in FIG. FIG. 11A and FIG. 11B show a DMD in which 1024 micromirror rows in which 1024 micromirrors are arranged in the main scanning direction are arranged in 756 pairs in the subscanning direction. DMD controlled to drive only the column, an imaging optical system composed of the projection lens and lens barrel shown in FIGS. 8A, 8B and 9, and a wedge prism pair shown in FIGS. An exposure apparatus provided with an exposure head having

  The lens barrel 400 shown in FIG. 9 is rotated to measure the exposure performance such as the focus and image quality of the two-dimensional pattern projected on the exposed surface of the photosensitive layer, and at the rotational position showing the best exposure performance. The lens barrel flange 410 and the bracket 420 were fixed, and the direction of the projection lens was fixed. Further, when the exposure of one frame is completed and the photosensitive layer (laminated body) moves by moving the stage in the scanning direction, the degree of waviness of the photosensitive layer in the exposure area changes. Focus adjustment was performed.

-Development-
Pure water was sprayed on the exposed substrate using a shower nozzle to uniformly wet the surface. Thereafter, shower development was performed using a KOH-based developer (Fuji Film Electronics Materials Co., Ltd., CDK-1). Development conditions are 23 ° C., 80 seconds, and a shear nozzle pressure of 0.04 MPa. Subsequently, the residue was removed by spraying pure water at a nozzle pressure of 9.8 MPa.

-Heat treatment-
The obtained image was heat-treated at 330 ° C. for 30 minutes to obtain a substrate in which circular pixels having a diameter of 20 μm were arranged on the entire surface at intervals of 100 μm.

(2) Formation of red (R) image Using the colored photosensitive resin composition R1 on the substrate on which the K image is formed, the heat-treated R image is formed by the same process as the formation of the black (K) image. Formed. The R1 photosensitive layer thickness was 1.5 μm, and the coating amount of the pigment (CI Pigment Red 254) was 0.274 g / m ² .

-Exposure process and development process-
The photosensitive layer R1 on the substrate was exposed in the same manner as the photosensitive layer K1. The exposure amount was 50 mJ / cm ² . For evaluation, a photosensitive layer R1 is similarly formed on a substrate on which K is not formed, and a color filter pattern, a resolution evaluation pattern (a pattern in which a large number of holes having different diameters are formed), and a step wedge are formed. The same processing was performed using the pattern. Thereafter, development was performed in the same manner as K.

(3) Formation of green (G) image The above-described colored photosensitive resin composition G1 is used on the substrate on which the K and R images are formed, and the heat-treated G is formed by the same process as the formation of the black (K) image. An image was formed. The G1 photosensitive layer thickness is 1.4 μm, the coating amount of the pigment (CI Pigment Green 36) is 0.355 g / m ² , and the coating amount of the pigment (CI Pigment Yellow 139) is 0.052 g. / M ² . Exposed and developed in the same manner as K. The exposure amount was equivalent to 40 mJ / cm ² .

(4) Formation of a blue (B) image Using the colored photosensitive resin composition B1 on a substrate on which the K, R, and G images are formed, heat treatment is performed in the same process as the formation of the black (K) image. A finished B image was formed to produce the desired color filter.
The film thickness of the B1 photosensitive layer was 1.4 μm, and the coating amount of pigment (CI Pigment Blue 15: 6) was 0.29 g / m ² . Exposed and developed in the same manner as K. The exposure amount was 50 mJ / cm ² .

Thereafter, the glass substrate 11 on which the R, G, and B pixels were formed was baked at 240 ° C. for 50 minutes to obtain a color filter 12.
Further, an ITO (Indium Tin Oxide) film 13 was formed thereon as a transparent electrode by sputtering to obtain a color filter substrate 10.

-Production of photosensitive transfer sheet for spacers-
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a coating solution for a thermoplastic resin layer having the following formulation A is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 6.0 μm. did.

[Prescription A for Coating Solution for Thermoplastic Resin Layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer ... 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], molecular weight 90,000)
Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane ... 39.0 parts-Surfactant 1 ... 10.0 parts-Methanol ... 90.0 parts- Methoxy-2-propanol: 51.0 parts ・ Methyl ethyl ketone: 700 parts

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol: 3.22 parts (PVA-205, saponification rate 80%, manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone: 1.49 parts (PVP K-30, manufactured by IS Japan Co., Ltd.)
・ Methanol: 42.3 parts ・ Distilled water: 524 parts

  Next, a photosensitive layer coating solution having the formulation 1 shown in Table 2 below was further applied onto the formed intermediate layer and dried to laminate a photosensitive layer having a dry layer thickness of 4.1 μm.

  As described above, a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer (total thickness of 3 layers is 11.6 μm) is formed, and then a cover film is further formed on the surface of the photosensitive layer. A polypropylene film having a thickness of 12 μm was heated, pressed and pasted to obtain a photosensitive transfer sheet for spacers.

In addition, the addition amount of each component in Table 2 is a mass part.
* Pigment-30% methyl isobutyl ketone dispersion of silica sol (trade name: MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.)
* Binder 4
・ Methacrylic acid / allyl methacrylate copolymer (= 20/80 [molar ratio], molecular weight 36,000; polymer substance)
* Coloring dyes ・ Victoria Pure Blue BOH-M (Hodogaya Chemical Co., Ltd.)

-Production of photo spacer-
The cover film of the obtained photosensitive transfer sheet for spacer (1) was peeled off, and the exposed surface of the photosensitive layer was superimposed on the ITO film of the color filter substrate 10 on which the ITO film prepared above was sputtered, Using a laminator Lamic II type [manufactured by Hitachi Industries, Ltd.], the films were bonded together at a conveying speed of 2 m / min under pressure and heating conditions of a linear pressure of 100 N / cm and 130 ° C. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive layer was transferred together with the thermoplastic resin layer and the intermediate layer (layer forming step).

Next, it exposed by the same method as K image. Next, KOH developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was sprayed from a flat nozzle at 23 ° C. and a nozzle pressure of 0.04 MPa for 80 seconds to perform shower development, and an unexposed portion was developed and removed. A pattern (spacer pattern) was obtained (patterning step).
The obtained spacer pattern was a transparent column having a diameter of 16 μm and an average height of 3.7 μm.

  Next, the color filter substrate provided with the spacer pattern was heat-treated at 230 ° C. for 30 minutes (heat treatment step) to produce a photospacer.

-Production of photosensitive transfer material for protrusions-
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a thermoplastic resin layer coating solution having the same formulation as the formulation A is applied and dried, and a thermoplastic resin having a dry film thickness of 15 μm is dried. A layer was provided. Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the same formulation as the formulation B was applied and dried to provide an intermediate layer having a dry film thickness of 1.6 μm. Next, a protrusion-forming coating liquid having the following formulation C is prepared, and this protrusion-forming coating liquid is applied onto the intermediate layer and dried to provide a liquid crystal alignment control protrusion having a dry film thickness of 2.0 μm. A photosensitive layer was coated. Further, a 12 μm-thick polypropylene film was attached to the surface of the photosensitive layer as a protective film. In this way, a photosensitive transfer material for protrusions was prepared by laminating a thermoplastic resin layer, an intermediate layer, a photosensitive layer for protrusions, and a protective film in this order from the PET temporary support side.

[Formulation C of projection forming coating liquid]
-Positive resist solution FH-2413F ... 53.3 parts (Fuji Film Electronics Materials Co., Ltd.)
・ Methyl ethyl ketone ・ ・ ・ 46.7 parts ・ Surfactant 1 ... 0.04 parts

-Formation of protrusions-
The protective film is peeled off from the photosensitive transfer material for protrusions obtained above, and the exposed surface of the exposed photosensitive layer for protrusions is superposed on the surface of the color filter substrate on which the ITO film is provided (on the color filter). Using a Lamic II type (manufactured by Hitachi Industries, Ltd.), lamination was performed under the conditions of a linear pressure of 100 N / cm, a temperature of 130 ° C., and a conveyance speed of 2.2 m / min. Thereafter, only the PET temporary support of the photosensitive transfer material for protrusions was peeled and removed at the interface with the thermoplastic resin layer. At this time, the photosensitive layer, the intermediate layer, and the thermoplastic resin layer are laminated in this order from the substrate side on the color filter substrate.

  Next, it exposed by the method similar to K image from the upper direction of the thermoplastic resin layer which is the outermost layer. Thereafter, a 1% triethanolamine aqueous solution was sprayed from above the thermoplastic resin at 30 ° C. for 30 seconds using a shower type developing device, and the thermoplastic resin layer and the intermediate layer were dissolved and removed. At this stage, the photosensitive layer for protrusions was not substantially developed. Subsequently, an aqueous solution containing 0.085 mol / L sodium carbonate, 0.085 mol / L sodium hydrogen carbonate and 1% sodium dibutylnaphthalenesulfonate is further sprayed at 33 ° C. for 30 seconds in a shower type developing device. While developing, unnecessary portions (uncured portions) of the protrusion photosensitive layer were developed and removed. As a result, protrusions made of a protrusion photosensitive layer patterned into a desired shape were formed on the color filter (RGB pixel). Next, the color filter substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes, thereby controlling the liquid crystal alignment with a height of 1.5 μm and a vertical cross-sectional shape on the color filter (RGB pixels). A protrusion was formed.

  Apart from the above, a TFT substrate was prepared as a counter substrate. An ITO (Indium Tin Oxide) film is formed on one surface of the TFT substrate by sputtering. Subsequently, an alignment film made of polyimide was provided on the ITO film of the TFT substrate and the ITO film on the side of the color filter substrate on which the photospacer was provided.

  Thereafter, an epoxy resin sealant was printed at a position corresponding to an outer frame of a black matrix provided around the pixel group of the color filter, and the color filter substrate was bonded to the TFT substrate. Next, the two bonded substrates were heat-treated to cure the sealing agent to obtain a laminate of the two substrates. The laminate was degassed under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates. After completion of the injection, a liquid crystal cell was obtained by applying an adhesive to the injection port portion and sealing by irradiation with ultraviolet rays.

A polarizing plate (HLC2-2518, manufactured by Sanritsu Co., Ltd.) was attached to both surfaces of the liquid crystal cell thus obtained. Next, a sidelight type backlight is configured using FR1112H as a red (R) LED, DG1112H as a green (G) LED, and DB1112H (both are chip-type LEDs manufactured by Stanley) as a blue (B) LED. The MVA mode liquid crystal display device of Reference Example 1 was prepared by arranging it on the side that would be the back surface of the liquid crystal cell provided with the polarizing plate.

(Example 2)
In Reference Example 1, a color filter of Example 2 was produced in the same manner as Reference Example 1 except that the direction of exposure was 45 ° between the coating direction and the scanning direction of the exposure head. Further, an MVA mode liquid crystal display device was assembled in the same manner as in Reference Example 1.

(Example 3)
In Reference Example 1, a color filter of Example 3 was produced in the same manner as Reference Example 1 except that the exposure direction was changed to the coating direction and the scanning direction of the exposure head was changed to 90 degrees. Further, an MVA mode liquid crystal display device was assembled in the same manner as in Reference Example 1.

(Comparative Example 1)
In Reference Example 1, a color filter of Comparative Example 1 was produced in the same manner as Reference Example 1, except that the autofocus mechanism was not turned on and operated. Further, an MVA mode liquid crystal display device was assembled in the same manner as in Reference Example 1.

(Comparative Example 2)
In Reference Example 1, the exposure method is the same as Reference Example 1 except that the exposure is performed through an exposure mask using an ultrahigh pressure mercury lamp, the exposure condition is 500 mJ / cm ² , and the distance between the coating layer and the exposure mask is 100 μm. Thus, a color filter of Comparative Example 2 was produced. Further, an MVA mode liquid crystal display device was assembled in the same manner as in Reference Example 1.

(Comparative Example 3)
Reference Example 1, except for changing the coating method of the photosensitive layer in a spin coater method, in the same manner as in Reference Example 1 to prepare a color filter of Comparative Example 1. As a result, due to the centrifugal force accompanying the rotation of the substrate, a large difference occurred in the thickness of the coating layer between the central portion and the peripheral portion of the substrate, making evaluation impossible.

For the obtained Reference Example 1, Examples 2 to 3 and Comparative Examples 1 and 2 , the line width variation of the pixel and the display quality were evaluated as follows. The results are shown in Table 3.

<Pixel line width variation>
Each obtained K image was photographed with a 500 × optical micrograph to measure the line width. The measurement was performed by randomly selecting 50 points in each of the vertical and horizontal directions, and was performed for a total of 100 points, and the width variation (obtained by dividing the standard deviation by the average) was calculated.

<Display quality>
Each of the obtained liquid crystal display devices displayed white. In this state, color unevenness was visually evaluated and ranked according to the following criteria. In addition, the thing of A and B rank is acceptable practically.
〔Evaluation criteria〕
A: Unevenness cannot be visually observed B: Unevenness cannot be visually observed C: Unevenness is visible from light D: Remarkable unevenness is visible

From the results of Table 3, in Reference Example 1 and Examples 2-3 , the width variation of the line drawing is smaller than in Comparative Examples 1-3 by combining slit coater application and digital exposure while performing autofocus. It can be seen that a high-quality image can be formed.

  The color filter manufactured by the method for manufacturing a color filter of the present invention has good display characteristics, and is particularly suitable for a liquid crystal display device (LCD) such as a portable terminal and a portable game machine. Address liquid crystal) and plasma display.

FIG. 1 is a schematic external view of the exposure apparatus. FIG. 2 is a schematic external view of the scanner. FIG. 3 is a diagram showing the internal configuration of the exposure head. FIG. 4 is a diagram illustrating a configuration of a light source unit as a light irradiation unit. FIG. 5 is a diagram showing the configuration of the laser emitting portion in the light irradiation means. FIG. 6 is a diagram showing the configuration of the LD module in the light irradiation means. FIG. 7 is an explanatory diagram of optical elements constituting the exposure head. FIG. 8A is a plan view showing a projection lens. FIG. 8B is another plan view showing the projection lens. FIG. 9 is a schematic side sectional view of a lens barrel including an imaging optical system and a schematic plan view of the lens barrel. FIG. 10 is a schematic perspective view of a DMD which is a light modulation means. FIG. 11A is an explanatory diagram of a use region of a micromirror that constitutes a DMD. FIG. 11B is an explanatory diagram of a use region of another micromirror that constitutes the DMD. FIG. 12 is a side view showing the configuration of a wedge-shaped prism pair that is a focus adjusting means. FIG. 13 is a schematic perspective view of a wedge-shaped prism pair which is a focus adjusting means. FIG. 14 is an explanatory diagram of optical elements constituting the exposure head. FIG. 15A is a diagram illustrating a configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 15B is a diagram illustrating another configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 16A is a diagram illustrating a configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 16B is a diagram illustrating another configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 17A is a perspective view schematically showing the positional relationship between the photosensitive material and the DMD. FIG. 17B is a side view schematically showing the positional relationship between the photosensitive material and the DMD.

Explanation of symbols

10 Exposure Device 30 Exposure Head 80 DMD
50 imaging optical system 51 first projection lens 52 second projection lens 54 wedge-shaped prism pair 12 photosensitive material

Claims (18)

A photosensitive layer forming step of forming a photosensitive layer by slit coating a photosensitive composition containing a binder, a polymerizable compound, and a photopolymerization initiator on the surface of the substrate;
The light from the exposure light source is modulated by the light modulation means that receives light from the exposure light source and modulates the light based on the pattern information, and the light modulated by the light modulation means is converted into an imaging means and a focus adjustment means. And an exposure step of performing exposure with autofocus while automatically focusing on the exposed surface of the photosensitive layer via the exposure layer, the direction of slit coater coating, and the scanning of the exposure head A method for producing a color filter, wherein an angle formed with a direction is set to 45 degrees to 90 degrees . 2. The method for producing a color filter according to claim 1, wherein an angle formed by the direction of slit coater application and the scanning direction of the exposure head is set to 45 degrees . 2. The method for producing a color filter according to claim 1, wherein an angle formed by the direction of slit coater application and the scanning direction of the exposure head is set to 90 degrees .   The imaging means forms an image of light modulated by the light modulation means in a substantially rectangular region whose long side is twice or more as long as the short side. Manufacturing method of color filter. The focus adjustment means has a wedge-shaped prism pair formed so that the thickness in the optical axis direction of the light modulated by the light modulation means changes,
5. The focal point when the light modulated by the light modulating means is imaged on the exposed surface of the photosensitive layer is adjusted by moving each wedge prism constituting the wedge prism pair. The manufacturing method of the color filter in any one of. The focus adjustment means has a microlens constituting an imaging optical system and a piezo element,
5. The focal point when the light modulated by the light modulation unit is imaged on the exposed surface of a photosensitive layer is adjusted by moving the microlens by the piezo element. Manufacturing method of color filter.   The imaging means is composed of either a lens that can rotate around the optical axis with respect to the optical axis of the light modulated by the light modulating means, or a lens that can move in a direction perpendicular to the optical axis. The method for producing a color filter according to claim 1.   The method for manufacturing a color filter according to claim 1, wherein the light modulation means is a spatial light modulation element.   The method for producing a color filter according to claim 1, wherein the exposure light source emits laser light emitted from the semiconductor laser element.   The exposure light source is a bundle-shaped fiber light source in which a plurality of optical fibers that allow a laser beam emitted from a semiconductor laser element to enter from one end and emit the incident laser beam from the other end are bundled. A method for producing a color filter according to claim 1.   The method for producing a color filter according to claim 1, wherein the exposure light source can synthesize and irradiate two or more lights.   An exposure light source condenses a plurality of lasers, a multimode optical fiber, and a laser beam emitted from each of the plurality of lasers by collimating them and converging them on an incident end face of the multimode optical fiber. The manufacturing method of the color filter in any one of Claim 1 to 11 which has a type | system | group. The manufacturing method of the color filter in any one of Claim 1 to 12 exposed using the light source whose illumination intensity is 100 mW / cm < ² > or more.   The method for producing a color filter according to claim 1, wherein the substrate has a size of 500 mm × 500 mm or more.   The method for producing a color filter according to claim 1, wherein the photosensitive composition is colored at least black (K).   For each color of R, G, and B in a predetermined arrangement on the surface of the substrate, using a photosensitive composition colored in at least three primary colors of red (R), green (G), and blue (B) The method for producing a color filter according to claim 1, wherein the color filter is formed by sequentially repeating the photosensitive layer forming step and the exposure step.   A color filter manufactured by the method for manufacturing a color filter according to claim 1. A liquid crystal display device using the color filter according to claim 17.