JP2007011231A - Pattern forming method, substrate with color filter, and display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method by which, when an ITO film is formed on the pattern, a ITO film with low resistance can be formed while keeping small changes in the resistance within the plane, and to provide a substrate with a color filter having pixels formed by the above pattern forming method, and to provide a display element having the substrate with a color filter. <P>SOLUTION: The pattern forming method for obtaining a pattern of a color filter through at least a resin layer forming step of forming a photosensitive resin layer comprising a photopolymerizable photosensitive resin composition on a substrate, a pattern exposure step of exposing the layer using a laser, a developing step of developing the photosensitive resin layer after pattern exposure, and a post-baking step of heat treating the photosensitive resin layer after development. The color filter of the substrate with a color filter is formed by the above forming method. The display element is equipped with the substrate with a color filter. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a display element used for a small mobile device, a large display, etc., a substrate with a color filter used for the display element, and a pattern forming method used for forming the color filter.

In recent years, liquid crystal display devices and organic EL display devices are being replaced with CRT displays because they are very compact and have the same or better performance as conventional CRT displays.
A color image displayed on such a display device is obtained by coloring light that has passed through a substrate made of a color filter made of a plurality of colors, an ITO (indium tin oxide) transparent conductive film, or the like to each color constituting the color filter. It is formed by combining a plurality of colors of light in an image-like manner. Currently, a color image is generally formed by pixels of three colors of red (R), green (G), and blue (B) that constitute a color filter.

  These pixels can be manufactured by a method such as forming a resin layer on a substrate, repeating exposure and development for the number of colors, and the conventional exposure is performed with a mercury lamp or the like using an exposure mask. A method of forming a pattern by exposure has been used. However, when pixels are formed by these exposure methods, in the ITO film formed on the pixels (pattern), the resistance value fluctuates in the plane, which becomes a difference in driving voltage, which is particularly large. In an area LCD panel or the like, it causes image color unevenness.

On the other hand, in recent years, maskless exposure using a laser or the like that can suppress in-plane variation of the ITO resistance value has been performed. As the maskless exposure, for example, a laser such as a semiconductor laser is used, and a method using a polygon mirror as a method of relative scanning while modulating light (for example, refer to Patent Document 1), DMD (digital micromirror) -A method using a device (for example, see Patent Document 2).
However, the exposure method using these lasers has a drawback that the resistance value of ITO becomes high. The ITO film needs to have a low resistance in order to drive the liquid crystal, and further improvement has been demanded.
JP 2002-523905 A JP 2004-56080 A

The present invention has been made in view of the above-mentioned conventional drawbacks.
That is, an object of the present invention is to provide a pattern forming method capable of forming a low-resistance ITO film while maintaining a small fluctuation in resistance in the surface when the ITO film is formed thereon, and the pattern. It is an object to provide a substrate with a color filter in which pixels are formed by a forming method, and a display element including the substrate with a color filter.

The above conventional problems are achieved by the present invention described below.
That is, the pattern forming method of the present invention is:
<1> A resin layer forming step (a) for providing a photosensitive resin layer made of a photopolymerizable photosensitive resin composition on a substrate, a pattern exposure step (b) for exposing the photosensitive resin layer with a laser, A color filter pattern is obtained through at least the development step (c) for developing the photosensitive resin layer after pattern exposure and the post-baking step (d) for heat-treating the photosensitive resin layer after development. And a pattern forming method.

  <2> The pattern forming step from the resin layer forming step (a) to the post-baking step (d) is repeated twice or more to provide two or more patterns on the substrate. <1 > The pattern forming method according to <1>.

  <3> The above <1> or <2 characterized by comprising a post-exposure step (e) for exposing the entire surface of the photosensitive resin layer between the development step (c) and the post-bake step (d). > The pattern forming method according to <1>.

  <4> The pattern forming method according to any one of <1> to <3>, wherein a temperature of the heat treatment in the post-baking step (d) is 180 ° C. or higher.

  <5> The pattern forming method according to <4>, wherein the temperature of the heat treatment is 180 to 260 ° C., and the temperature is raised from room temperature to the temperature over 5 to 60 minutes.

  <6> The pattern forming method according to <4> or <5>, wherein the heating time at the heat treatment temperature is 10 to 300 minutes.

  <7> The pattern formation according to any one of <2> to <6>, wherein at least three colored patterns of red (R), green (G), and blue (B) are provided. Is the method.

Moreover, the substrate with a color filter of the present invention is <8> with a color filter, wherein colored pixels are formed on the substrate by the pattern forming method according to any one of <1> to <7>. It is a substrate.

  <9> The substrate with a color filter according to <8>, wherein an ITO transparent electrode is formed.

Furthermore, the display element of the present invention is
<10> A display element comprising the substrate with a color filter according to <8> or <9>.

  According to the present invention, when an ITO film is formed thereon, a pattern forming method capable of forming a low resistance ITO film while maintaining a small resistance fluctuation in the surface, and the pattern forming method Thus, it is possible to provide a substrate with a color filter in which pixels are formed, and a display element including the substrate with a color filter.

The pattern forming method of the present invention includes a resin layer forming step (a) in which a photosensitive resin layer composed of a photopolymerizable photosensitive resin composition is provided on a substrate, a pattern exposure step (b) in which exposure is performed with a laser, and a laser. It has at least a development step (c) for developing the photosensitive resin layer after exposure and a post-baking step (d) for heat-treating the photosensitive resin layer after development.
By forming a color filter pattern by the above method, the ITO film when an ITO film is provided on the pattern can be made a low-resistance ITO film while suppressing fluctuations in resistance value in the plane. it can.

The resistance value of the ITO film is preferably 30Ω / □ or less from the viewpoint of satisfactorily driving the liquid crystal or the like in the display element, and more preferably 20Ω / □ or less when used for a large area LCD panel or the like. The lower limit is generally 5Ω / □ or more as a range in which the production is possible.
Further, the in-plane variation of the ITO resistance value is preferably less than 10%, and more preferably 5% or less, from the viewpoint of suppressing the difference in drive voltage and preventing the occurrence of color unevenness. The lower limit is generally 1% or more as a range in which the production is possible.

Here, in the present invention, the resistance value of the ITO film was measured by a four-terminal method using a Loresta manufactured by Mitsubishi Yuka Co., Ltd. A specific measuring method will be described. The Loresta 4-terminal probe was pressure-bonded to a sample prepared in an environment of 23 ° C. and 65% humidity, and the measurement was performed at 5V.
The in-plane variation of the ITO resistance value was obtained by randomly measuring the ITO resistance within the surface of the 500 × 600 mm ITO fabrication substrate based on the above resistance value measurement method.
Hereinafter, in describing the present invention in detail, a pattern forming method will be described in detail, and then a substrate with a color filter and a display element will be described.

<Pattern formation method>
The pattern in the present invention is formed using a photopolymerization type photosensitive resin composition (hereinafter sometimes simply referred to as “resin composition”), and two or more types of patterns are formed on the substrate. Even one that forms one kind of pattern may be used. In addition, as a color filter, it is preferable to form pixels (patterns) of three colors of red (R), green (G), and blue (B), and if necessary, a pattern of black matrix (K) is further formed. Is also preferable.

  The pattern forming method includes a resin layer forming step (a) for forming a resin layer on a substrate, a pattern exposure step (b) for exposing with a laser, a developing step (c) for developing, and a resin layer after development. And a post-baking step (d) for heat-treating, and can be formed by repeating these steps for the number of types of patterns (for example, the number of colors). Further, it is also preferable to perform a post-exposure step (e) in which the entire surface of the resin layer is exposed after the development step (c) if necessary.

(Resin layer forming step (a))
In the above pattern forming method, as a method of forming a resin layer on the substrate, (a-1) a method of applying a resin composition by a known application device or the like, and (a-2) using a resin transfer material, The method of pasting with a laminator is mentioned. Only the coating method and the laminating method will be described here, and the resin composition and the resin transfer material will be described in detail later.

(A-1) Application by coating apparatus In the pattern forming method of the present invention, the resin composition is applied by a known application method such as spin coating, curtain coating, slit coating, dip coating, air knife coating. A method such as a coating method, a roller coating method, a wire bar coating method, a gravure coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294 can be used. In particular, a slit coating method in which coating is performed by a slit-like nozzle (slit coater) having a slit-like hole in a portion from which the liquid is discharged is preferably used. Preferred examples of the slit-shaped nozzle include Japanese Patent Application Laid-Open Nos. 2004-89851, 2004-17043, 2003-170098, 2003-164787, and 2003-10767. Slit nozzles and slit coaters described in Japanese Laid-Open Patent Publication No. 2002-79163, Japanese Laid-Open Patent Publication No. 2001-310147, and the like.
When the resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.0 to 2.0 μm.

  In the pattern forming method of the present invention, when the resin layer is formed by application of the resin composition, an oxygen barrier film is further formed on the resin layer for the purpose of increasing exposure sensitivity in the pattern exposure process described later. Can be provided. Examples of the oxygen-blocking film include the same ones as described in the section of (Intermediate layer) of <Resin transfer material> described later. Although not particularly limited, the thickness of the oxygen blocking film is preferably 0.5 to 3.0 μm.

(A-2) Affixing by a laminator Affixed on a substrate by using a resin or transfer material described later, heating and / or pressurizing a resin layer formed into a film, using a roller or a flat plate, and pressing or thermocompression bonding. Can be attached. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575.

  (Pattern exposure process (b))

The pattern exposure in the present invention is a maskless exposure using a laser as a light source, and is two-dimensional by performing relative scanning while modulating light based on image data using a spatial light modulation device arranged in two dimensions. Image formation is performed.
An object called a “mask” in which an image (pattern) is formed with a material that does not transmit or weakly transmits exposure light is disposed in the optical path of the exposure light, and the resin layer is exposed in a pattern corresponding to the image. In contrast to the conventional exposure method (referred to as mask exposure), the maskless exposure is an exposure method in which the resin layer is exposed in a pattern without using the “mask”.

-Laser description-
In the pattern exposure of the present invention, a laser is used as a light source.
Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Irradiation is performed by an oscillator and an amplifier that produce monochromatic light having stronger coherence and directivity by amplifying and oscillating light waves using the phenomenon of stimulated emission that occurs in a material having an inversion distribution. Examples of excitation media include crystals, glass, liquids, dyes, and gases. From these media, solid lasers (YAG lasers), liquid lasers, and gas lasers (argon lasers, He-Ne lasers, carbon dioxide gas lasers, and excimer lasers). A known laser such as a semiconductor laser can be used.

  The semiconductor laser is a light emitting diode that stimulates and emits coherent light at the pn junction when electrons and holes flow out to the junction by carrier injection, excitation by electron beam, ionization by collision, photoexcitation, etc. It is a laser using. The wavelength of the emitted coherent light is determined by the semiconductor compound.

The wavelength of the laser used in the present invention is not particularly limited, but in particular, from the viewpoint of resolution and cost of the laser device, and availability, the semiconductor laser is preferably selected from a wavelength range of 300 to 500 nm, 340 to 450 nm is more preferable, and 360 to 415 nm is particularly preferable.
In the solid laser, 532 nm of YAG-SHG solid laser is preferable. Further, semiconductor-excited solid-state lasers include 532, 355, and 266 nm. Among them, 355 nm is preferably selected in that the conventional photopolymerization initiator for resist has sensitivity. In the gas laser, 249 nm of KrF laser and 193 nm of ArF laser are preferably used.
Among these light sources, considering the case where the photosensitive material is exposed in the manufacturing process of the display device, it is preferable to select a light source having an exposure wavelength of 405 nm from the viewpoint of increasing the transmittance of the display region.

The beam diameter of the laser is not particularly limited, but among them, from the viewpoint of pattern resolution, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
Although it does not specifically limit as energy amount of a laser beam, From a viewpoint of exposure time and resolution, 1-100 mJ / cm < ² > is preferable especially and 5-20 mJ / cm < ² > is more preferable.

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

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

As a method of performing relative scanning while modulating light of the present invention, for example, the following method can also be applied.
An example of drawing using a polygon mirror described in Japanese Patent Laid-Open No. 5-150175, an apparatus using a polygon mirror by visually acquiring a part of an image of a lower layer described in JP-T-2004-523101 (WO2002 / 039793) In this example, exposure is performed with the position of the upper layer aligned with the position of the lower layer, exposure using the DMD described in JP-A-2004-56080, exposure apparatus including the polygon mirror described in JP-T-2002-523905, An exposure apparatus having a polygon mirror described in 2001-255661, an example in which DMD, LD, and multiple exposure described in Japanese Patent Application Laid-Open No. 2003-50469 are combined, and an exposure whose exposure amount is changed depending on the part of the substrate described in Japanese Patent Application Laid-Open No. 2003-156853 Examples of the method include an example of an exposure method for performing misalignment adjustment described in JP-A-2005-43576.

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

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

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

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

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

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

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

  The lens system 67 includes a pair of combination lenses 71 that collimate the laser light emitted from the fiber array light source 66 and a pair of combination lenses that correct the light quantity distribution of the collimated laser light to be uniform. 73 and a condensing lens 75 that condenses the laser light whose light quantity distribution has been corrected on the DMD 50. With respect to the arrangement direction of the laser emitting end, the combination lens 73 spreads the light beam at a portion close to the optical axis of the lens and contracts the light beam at a portion away from the optical axis, and with respect to a direction orthogonal to the arrangement direction. Has a function of allowing light to pass through as it is, and corrects the laser light so that the light quantity distribution is uniform.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Development process (c))
There is no restriction | limiting in particular as a developing solution to be used, A well-known developing solution, such as what is described in Unexamined-Japanese-Patent No. 5-72724, can be used. The developer preferably has a resin-type developing behavior such as a resin layer. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable, but is further miscible with water. A small amount of an organic solvent having
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed resin layer by shower. In addition, it is preferable to spray an alkaline solution having a low solubility of the resin layer by a shower or the like before development 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.
As the cleaning solution, known ones can be used (including phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name "T-SD1 (manufactured by Fuji Photo Film)", or sodium carbonate, Phenoxyoxyethylene surfactant-containing, trade name “T-SD2 (manufactured by Fuji Photo Film)”) is preferable.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

(Post exposure process (e))
In order to further cure the resin layer developed in the developing step, it is preferable to perform post exposure in the pattern forming method of the present invention. Here, as the light source used for the post-exposure, any light source capable of irradiating light in a wavelength region that can cure the resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are particularly preferably used. As an exposure amount, it is 10-10000 mJ / cm < ² > normally, Preferably it is 100-1000 mJ / cm < ² >.

(Post bake process (d))
After forming the pattern in the present invention, post-baking is performed in the pattern forming method of the present invention in order to make the ITO film formed thereon have a desired low resistance.
The post-baking temperature is preferably 180 ° C. or more, more preferably 180 to 260 ° C. from the viewpoint of more effectively preventing cracks during ITO film formation and thereby obtaining a desired resistance value. In particular, 200 ° C to 240 ° C is preferable. The time is preferably 10 to 300 minutes while maintaining the above temperature, more preferably 15 to 200 minutes, and particularly preferably 20 to 150 minutes.
Further, in order to more effectively prevent the occurrence of the cracks, it is preferable to gradually raise the temperature from room temperature to the post-bake temperature, specifically 1 to 100 minutes at a constant rate, and further 5 to 60. It is preferable that the temperature is raised to the above temperature over 5 minutes, particularly 5 to 20 minutes.

  The pattern according to the present invention is formed as described above. For example, when the resin composition is sequentially applied and overlapped as in the formation of a color filter composed of four colors of K (black), R, G, and B, In some cases, the thickness of the coating liquid may be reduced due to the leveling of the coating solution. For this reason, it is preferable to further divide the divisional alignment protrusions on the pattern. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, it is preferable that three or two colors be overlapped because the thickness is kept constant.

<Photopolymerization type photosensitive resin composition>
Subsequently, the resin composition used for the pattern formation method of this invention is demonstrated.
The resin composition includes (1) an alkali-soluble resin, (2) a monomer or oligomer, (3) a photopolymerization initiator or photopolymerization initiator system, and (4) a colorant. A resin composition is preferred.
Hereinafter, these components (1) to (4) will be sequentially described.

(1) Alkali-soluble resin As the alkali-soluble resin (hereinafter sometimes simply referred to as “binder”) in the present invention, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. The binder polymer having these polar groups may be used alone, or may be used in the state of a composition used in combination with a normal film-forming polymer, and the content of the resin composition relative to the total solid content is 20-50 mass% is common and 25-45 mass% is preferable.

(2) Monomer or Oligomer The monomer or oligomer in the present invention is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. preferable.

(3) Photopolymerization initiator or photopolymerization initiator system As a method for curing the resin composition, a photopolymerization initiator or a photopolymerization initiation system is used in the present invention. The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray (also referred to as exposure). It is a compound to be obtained and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.
For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

Specifically, a trihalomethyl group-substituted trihalomethyloxazole derivative or s-triazine derivative described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, A trihalomethyl group-containing compound such as the trihalomethyloxadiazole compound described in Japanese Patent No. 4221976;
9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;
6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazine compounds such as trichloromethyl) -s-triazine;
In addition, 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2'-bis (2,4-dichlorophenyl) -4,4 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and in particular, a biimidazole compound, a trihalomethyl group-containing compound, and an acridine system It is preferable to contain at least one selected from compounds. Biimidazole compounds, trihalomethyl group-containing compounds, and acridine compounds are also useful in that they are versatile and inexpensive.

  Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. The total amount of the photopolymerization initiator in the resin composition is preferably 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content (mass) of the resin composition. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

A sensitizer can be added in addition to the photopolymerization initiator for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to the resin layer.
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means.
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 (for example, pyrene, perylene, triphenylene), Xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines ( For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squariums (for example, squalium), acridones (for example, acridone) Chloroacridone, N-methylacridone, N-butylacridone, 10-N-butyl-2-chloroacridone, 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′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2 -Furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7 Examples thereof include diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, as well as JP-A-5-19475 and JP-A-7-271028. And JP-A 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 resin composition, 0.1-20 mass% is more preferable, 0.2-10 mass % Is particularly preferred. When the content is 0.05% by mass or more, the sensitivity to active energy rays is improved, the exposure process time can be shortened, and the productivity can be improved. On the other hand, by being 30 mass% or less, sensitizer precipitation from the resin layer at the time of storage can be effectively prevented.

  The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. The “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

  The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor). The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2. , 5-dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

  Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.

  The hydrogen donor can be used alone or in admixture of two or more, and the formed image is less likely to fall off from the permanent support during development, and can be improved in strength and sensitivity. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzobenzone. Thiazole / 4,4′-bis (diethylamino) benzophenone.

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. The total amount of the hydrogen donor in the resin composition is preferably 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content (mass) of the resin composition.

(4) Colorant The colorant in the present invention includes C.I. in the R (red) resin composition. I. Pigment Red (C.I.P.R.) 254 is C.I. in the G (green) resin composition. I. Pigment Green (C.I.P.G.) 36 is C.I. in the B (blue) resin composition. I. CI Pigment Blue (C.I.P.B.) 15: 6 is a preferred example.

In addition to the above-mentioned pigments, known dyes, pigments and the like having the color index (CI) numbers described below can be mentioned. In addition, when using a pigment among this well-known coloring agent, it is desirable that it is uniformly disperse | distributed in a resin composition, Therefore A particle size should be 0.1 micrometer or less, especially 0.08 micrometer or less. preferable.
Specific examples of the known dyes or pigments include the pigments and dyes described in JP-A-2005-17716 [0038] to [0054] and JP-A-2004-361447 [0068]. To [0072] and the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

  In the present invention, the combination of the above-described pigments preferably used in combination is C.I. I. In pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment yellow 139 or C.I. I. A combination with CI Pigment Violet 23; I. In Pigment Green 36, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138 or C.I. I. A combination with CI Pigment Yellow 180; I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23 or C.I. I. A combination with Pigment Blue 60 is mentioned.

  As described above, C.I. I. Pigment Red. 254, C.I. I. P. G. 36, C.I. I. P. B. The content of 15: 6 is C.I. I. Pigment Red. 254 is preferably 80% by mass or more, and particularly preferably 90% by mass or more. C. I. P. G. 36 is preferably 50% by mass or more, particularly preferably 60% by mass or more. , C.I. I. P. B. 15: 6 is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

  The pigment is preferably a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), which is dissolved and diluted. Component (organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, page 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, it may be finely pulverized by frictional force by mechanical grinding described in page 310 of the document.

  The colorant (pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. When the number average particle diameter of the pigment is less than 0.001 μm, the particle surface energy is increased and the particles are easily aggregated, so that it is difficult to disperse the pigment and it is difficult to keep the dispersion state stable. On the other hand, when the number average particle diameter exceeds 0.1 μm, the polarization is canceled by the pigment, and the contrast is lowered. As used herein, the term “particle size” refers to the diameter when an electron micrograph image is a circle of the same area, and “number average particle size” refers to the number of particles obtained by determining the particle size. Say 100 average value.

  The particle size can be reduced by adjusting the dispersion time of the pigment dispersion. For the dispersion, the known dispersers described above can be used, and the dispersion time is preferably 10 to 30 hours, more preferably 18 to 30 hours, and most preferably 24 to 30 hours. When the dispersion time is less than 10 hours, the pigment particle size is large and the polarization may be canceled by the pigment, which may lower the contrast. On the other hand, when the dispersion time exceeds 30 hours, the viscosity of the dispersion liquid increases and application may be difficult.

(Other additives)
-Solvent-
In the resin composition of the present invention, an organic solvent may be used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

-Surfactant-
In the case of forming a conventional color filter, there is a problem that the color of each pixel becomes dark in order to achieve high color purity, and the uneven film thickness of the pixel is recognized as the color unevenness as it is. For this reason, it has been demanded to improve the film thickness variation during the formation (application) of the resin layer, which directly affects the pixel film thickness.
In the present invention, it is preferable to contain an appropriate surfactant in the resin composition from the viewpoint that it can be controlled to a uniform film thickness and effectively prevent coating unevenness (color unevenness due to film thickness fluctuation). . Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.

-Thermal polymerization inhibitor-
The resin composition of the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

-UV absorber-
The resin composition of the present invention may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like 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-dihydroxybenzophenone, 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-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like.

  Moreover, in the resin composition in this invention, other than the said additive, the "adhesion adjuvant" of Unexamined-Japanese-Patent No. 11-133600, another additive, etc. can be contained.

<Resin transfer material>
Next, the resin transfer material used in the pattern forming method of the present invention will be described.
The resin transfer material is preferably formed using a resin transfer material described in JP-A-5-72724, that is, an integral film. Examples of the constitution of the integrated film include temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film, temporary support / thermoplastic resin layer / photosensitive resin layer / protective film. A structure in which layers are stacked in order is preferable.
In addition, it is essential for this resin transfer material to provide the photosensitive resin layer of the said photosensitive resin composition.

-Temporary support-
The temporary support for the resin transfer material needs to be flexible and not to cause significant deformation, shrinkage, or elongation even under pressure or pressure and heating. Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.
The thickness of the temporary support is not particularly limited, but is generally in the range of 5 to 200 μm, and particularly in the range of 10 to 150 μm is advantageous and preferable from the viewpoint of ease of handling and versatility. Further, the temporary support may be transparent, or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like.

-Thermoplastic resin layer-
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. 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 and 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 polymeric polyamide resins such as N- dimethylamino nylon.

-Intermediate layer-
In the resin transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

-Protective film-
A thin protective film is preferably provided on the resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

-Preparation method of resin transfer material-
The resin transfer material in the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support, followed by drying. Apply and dry a solution of an intermediate layer material composed of a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, and then apply the photosensitive resin layer of the photosensitive resin composition with a solvent that does not dissolve the intermediate layer, It can be produced by drying.
Also, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.
In the resin transfer material, the thickness of the photosensitive resin layer of the photosensitive resin composition is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and 1.0 to 3. 0 μm is particularly preferable.
Further, although not particularly limited, preferred film thicknesses of the other layers are preferably 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and 4 to 40 μm for the protective film. .

  The application in the method for producing the resin transfer material can be performed by a known application apparatus or the like listed in the section (resin layer forming step) in the <pattern forming method>. In the present invention, In particular, it is preferably performed by a coating apparatus (slit coater) using a slit-like nozzle.

<Board>
As the substrate used in the pattern forming method of the present invention, for example, a transparent substrate is used, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, or the like. And a plastic film.
Moreover, the said board | substrate can make close_contact | adherence favorable with a resin composition or a resin transcription | transfer material by giving a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.

<ITO transparent electrode>
The pattern provided on the substrate by the pattern forming method described above has an effect that when an ITO transparent electrode (ITO film) is formed thereon, an ITO film having a low resistance and a small in-plane resistance value variation can be obtained. .
Here, the formation of the ITO film can be performed by appropriately selecting a commonly used known method. For example, the ITO film can be formed by sputtering ITO using a sputtering apparatus. In addition, from the viewpoint of obtaining an ITO film with lower resistance and smaller in-plane resistance variation, the sputtering condition is preferably a vacuum of 1 × 10 ⁻³ Pa or less, 1 × 10 ⁻⁵ Pa or less is more preferable. The acceleration voltage is preferably 1 kV to 100 kV, more preferably 5 kV to 50 kV. The temperature is preferably from 100 to 300 ° C, particularly preferably from 150 to 250 ° C. The ITO film obtained by the above method preferably has a thickness of 500 to 5000 mm, more preferably 1000 to 3000 mm, from the viewpoint of resistance and transparency.

<Substrate with color filter and display element>
The substrate with a color filter of the present invention is characterized in that pixels of a color filter are formed by the above-described pattern forming method, and an aspect in which an ITO film is formed on the color filter may be employed.
In forming the color filter, as described in JP-A Nos. 11-248921 and 3255107, a base is formed by stacking resin compositions that form the color filter, and a transparent electrode ( It is preferable from the viewpoint of cost reduction to form a spacer by forming an ITO film) and further superimposing projections for split orientation.

  In addition, the display element (display device) of the present invention is not particularly limited as long as it includes the substrate with the color filter, and examples thereof include a liquid crystal display element and an organic EL element. Liquid crystal display devices include ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optical Liquid Crystal). Various display modes such as Vertically Aligned), HAN (Hybrid Aligned Nematic), and GH (Guest Host) can be adopted, and it can be suitably used for large-screen liquid crystal display devices such as notebook PC displays and TV monitors. it can.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these Examples. Unless otherwise specified, “parts”, “%”, and “molecular weight” below represent “parts by mass”, “mass%”, and “mass average molecular weight”.

Example 1
[Preparation of color filter substrate with ITO]
-Production of photosensitive resin transfer material-
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, a colored photosensitive resin composition K1 having a composition of formulation K1 described in Table 1 below is applied and dried, a thermoplastic resin layer having a dry film thickness of 14.6 μm on the temporary support, and a dry film thickness. Was provided with an intermediate layer having a thickness of 1.6 μm and a photosensitive resin layer having a dry film thickness of 2.4 μm, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer are integrated is prepared, and the sample name is the photosensitive resin transfer material. It was set as K1.

Coating liquid for thermoplastic resin layer: Formulation H1
・ Methanol 11.1 parts ・ Propylene glycol monomethyl ether acetate 6.36 parts ・ Methyl ethyl ketone 52.4 parts ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight = 10,000, Tg ≈ 100 ° C) 13.6 parts · Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (Shin Nakamura Chemical Co., Ltd., 2, 2- Screw [4-
(Methacryloxypolyethoxy) phenyl] propane) 9.1 parts. Surfactant 1 (Dainippon Ink Chemical Co., Ltd., trade name: Megafax F780F)
0.54 parts

Intermediate layer coating solution: Formulation P1
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts · Polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd., K-30) 14.9 parts · Distilled water 524 parts · Methanol 429 parts

  Next, the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1 is changed to the following colored photosensitive resin compositions R1, G1, and B1 having the composition described in Table 1 below. Other than that, photosensitive resin transfer materials R1, G1, and B1 were prepared in the same manner as described above.

-Formation of black (K) image-
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), rubber roller temperature 130 ° C., linear pressure Lamination was performed at 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the protective film, pattern exposure with a laser was performed. Specifically, the exposure was performed by a semiconductor laser having a central wavelength of 405 nm through an optical system having an optical path parallel to the (1 W) film surface. The exposure amount was 40 mJ / cm ² .

  Next, with a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer.

Subsequently, a sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa, and the photosensitive resin layer was developed to obtain a patterning image.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.)”), 33 ° C., 20 seconds, cone type Residue removal was performed with a rotating brush having a shower and nylon bristles at a nozzle pressure of 0.02 MPa to obtain a black (K) image.

Thereafter, the substrate was further heated from room temperature to 220 ° C. at a constant rate for 5 minutes, and then heat-treated (post-baked) at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Formation of red (R) pixels-
Using the photosensitive resin transfer material R1, a red (R) pixel was obtained on a substrate on which a black (K) pixel was formed by the same process as the photosensitive resin transfer material K1. However, the exposure amount of pattern exposure was 20 mJ / cm ² , and development with a sodium carbonate-based developer was 35 ° C. for 35 seconds.

The photosensitive resin layer R1 has a thickness of 2.0 μm. I. Pigment red 254 and C.I. I. Pigment Red. The coating amount of 177 was 0.88 and 0.22 g / m ² , respectively.
The substrate on which the R pixel was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Formation of green (G) pixels-
Using the photosensitive resin transfer material G1, green (G) pixels were obtained on the substrate on which the red (R) pixels were formed, in the same process as the photosensitive resin transfer material R1. However, the exposure amount of pattern exposure was 20 mJ / cm ² , and development with a sodium carbonate developer was 34 ° C. and 45 seconds.
The photosensitive resin layer G1 has a thickness of 2.0 μm. I. Pigment green 36 and C.I. I. The coating amounts of Pigment Yellow 150 were 1.12 and 0.48 g / m ² , respectively.
The substrate on which the R and G images were formed was again washed with a brush as described above, and after pure water shower cleaning, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Formation of blue (B) pixels-
Using the photosensitive resin transfer material B1, a blue (B) pixel is obtained on the substrate on which the red (R) pixel and the green (G) pixel are formed in the same process as the photosensitive resin transfer material R1. It was. However, the exposure amount of pattern exposure was 10 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds.
The photosensitive resin layer B1 has a thickness of 2.0 μm. Pigment Blue 15: 6 and C.I. I. The coating amounts of Pigment Violet 23 were 0.63 and 0.07 g / m ² , respectively.
The substrate on which the R, G, B, and K images were formed was baked at 240 ° C. for 50 minutes to obtain the desired color filter.

Here, the preparation of the colored photosensitive resin compositions K1, R1, G1, and B1 shown in Table 1 will be described.
The colored photosensitive resin composition K1 is first weighed in K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, methyl ethyl ketone, binder 1, DPHA solution, B-CIM (2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, Hodogaya Chemical Kogyo Co., Ltd.), NBCA (manufactured by Kurokin Chemical), N-phenylmercaptobenzimidazole, hydroquinone monomethyl ether and surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.), and a temperature of 40 ° C. It is obtained by stirring at 150 rpm at (± 2 ° C.) for 30 minutes.

Of the compositions described in Formula K1,
The composition of K pigment dispersion 1 is
・ Carbon black (Degussa, trade name Special Black 250) 13.1 parts
N, N′-bis- (3-diethylaminopropyl) -5- {4-
[2-oxo-1- (2-oxo-2,3-dihydro-1H-
Benzimidazol-5-ylcarbamoyl) -propylazo]
-Benzoylamino} -isophthalamide 0.65 parts
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, molecular weight 37,000) 6.72 parts
・ 79.53 parts of propylene glycol monomethyl ether acetate

  The colored photosensitive resin composition R1 was first weighed in the amounts of R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 rpm for 10 minutes, then methyl ethyl ketone, binder 2, DPHA solution, B-CIM (2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetra Weigh phenyl-1,2'-biimidazole (Hodogaya Chemical Co., Ltd.), NBCA (10-n-butyl-2-chloroacridone, Kurogane Kasei), N-phenylmercaptobenzimidazole, phenothiazine , Added in this order at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 30 minutes, and weighed out the surfactant 1 in the amount shown in Table 1, ± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200.

Of the compositions listed in Table 1,
The composition of the R pigment dispersion 1 is
・ C. I. P. R. 254 8 parts
N, N'-bis- (3-diethylaminopropyl) -5- {4- [2
-Oxo-1- (2-oxo-2,3-dihydro-1H-benzimidazol-5-ylcarbamoyl) -propylazo] -benzoylamino}
-0.8 parts isophthalamide
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, molecular weight 37,000) 8 parts
Propylene glycol monomethyl ether acetate 83.2 parts

The composition of the R pigment dispersion 2 is
・ C. I. P. R. 177 18 parts
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, molecular weight 37,000) 12 parts
・ 70 parts of propylene glycol monomethyl ether acetate
It is.
The above composition was dispersed with a motor mill M-50 (manufactured by Eiger) and zirconia beads having a diameter of 0.65 mm for 27 hours at a peripheral speed of 9 m / s to prepare a pigment dispersion.

  The colored photosensitive resin composition G1 is first weighed in the amounts of G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, and mixed at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, cyclohexanone, DPHA solution, B-CIM (manufactured by Hodogaya Chemical), NBCA (manufactured by Kurokin Chemical), N-phenylmercaptobenzimidazole, and phenothiazine in the amounts shown in Table 1 were added. Weigh out and add in this order at a temperature of 24 ° C. (± 2 ° C.) and stir at 150 rpm for 30 minutes. It is obtained by adding and stirring at 30 rpm for 5 minutes and filtering through nylon mesh # 200.

Of the compositions listed in Table 1,
The composition of G pigment dispersion 1 is
・ C. I. P. G. 36 14 parts
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, molecular weight 37,000) 23 parts
N, N′-bis- (3-diethylaminopropyl) -5- {4- [2-oxo-1- (2-oxo-2,3-dihydro-1H-benzimidazole-5
Ylcarbamoyl] -propylazo] -benzoylamino} -isophthalamide
1.4 parts
・ Propylene glycol monomethyl ether acetate 61.6 parts
It is.

The composition of the Y pigment dispersion 1 is
・ C. I. P. Y. 150 15 parts
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, molecular weight 37,000) 9 parts
N, N′-bis- (3-diethylaminopropyl) -5- {4- [2-oxo-1- (2-oxo-2,3-dihydro-1H-benzimidazole-5
Ylcarbamoyl) -propylazo] -benzoylamino} -isophthalamide
1.5 parts
・ 74.5 parts of propylene glycol monomethyl ether acetate
It is. The above composition was dispersed for 28 hours at a peripheral speed of 9 m / s using a motor mill M-50 (manufactured by Eiger) and zirconia beads having a diameter of 0.65 mm to prepare a pigment dispersion.

  The colored photosensitive resin composition B1 is first weighed in the amount of B pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, methyl ethyl ketone, binder 3, DPHA solution, B-CIM (made by Hodogaya Chemical), NBCA (made by Kurokin Chemical), N-phenyl mercaptobenzimidazole, and phenothiazine are weighed out at a temperature of 25 ° C. (± 2 ° C.). Add in this order, stir at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes, and weigh out the amount of surfactant 1 listed in Table 1 and add at a temperature of 24 ° C. (± 2 ° C.). And stirred at 30 rpm for 5 minutes and filtered through nylon mesh # 200.

Of the compositions listed in Table 1,
The composition of the B pigment dispersion 1 is
・ C. I. P. B. 15: 6 11.28 parts
・ C. I. P. V. 23 0.72 parts
・ EFKA-745 (manufactured by EFKA ADDITIVES BV) 0.6 parts
・ Disparon DA-725 (Enomoto Kasei Co., Ltd.) 0.75 parts
Propylene glycol monomethyl ether acetate 86.65 parts
It is. The above composition was dispersed with a motor mill M-50 (manufactured by Eiger) and zirconia beads having a diameter of 0.65 mm for 27 hours at a peripheral speed of 9 m / s to prepare a pigment dispersion.

In addition, among the compositions described in Table 1,
The composition of binder 1 is
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22
Random copolymer of molar ratio, molecular weight 37,000) 27 parts
・ Propylene glycol monomethyl ether acetate 73 parts

The composition of binder 2 is
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate)
= Random copolymer of 38/25/37 molar ratio,
(Molecular weight 38,000) 27 parts
・ Propylene glycol monomethyl ether acetate 73 parts

The composition of binder 3 is
-Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts
・ Propylene glycol monomethyl ether acetate 73 parts
It is.

The composition of the DPHA solution is
Dipentaerythritol hexaacrylate (polymerization inhibitor MEHQ 500 ppm
Contained, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts
・ Propylene glycol monomethyl ether acetate 24 parts
・ Surfactant 1 (Dainippon Ink Chemical Co., Ltd., trade name: MegaFuck F780F)
30 copies
・ Methyl ethyl ketone 70 parts
It is.

The composition of Surfactant 1 (Dainippon Ink Chemical Co., Ltd., trade name: Megafac F780F)
_{· C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts of _{H (OCH (CH 3) CH} 2) between ₇ OCOCH = CH ₂ 55 parts of _{H (OCH 2 CH 2) 7} OCOCH = CH 2 5 parts Copolymer,
(Molecular weight 30,000) 30 parts
-70 parts of methyl ethyl ketone.

On the color filter pixels obtained above, ITO (Indium Tin Oxide) was sputtered at a temperature of 200 ° C. at a vacuum of 1 × 10 ⁻⁴ Pa and an acceleration voltage of 40 kV using a sputtering device (SIH3030, ULVAC). Then, an ITO film having a thickness of 2000 mm was formed to produce a color filter substrate with ITO.

[Evaluation]
-ITO resistance and in-plane variation-
The ITO resistance value of the color filter substrate with ITO was measured by a four-terminal method using Loresta manufactured by Mitsubishi Yuka Co., Ltd. Specifically, the Loresta 4-terminal probe was pressure-bonded to a sample prepared in an environment of 23 ° C. and 65% humidity, and the measurement was performed at 5V.
The in-plane variation of the ITO resistance value was obtained by randomly measuring the ITO resistance within the surface of the 500 × 600 mm ITO fabrication substrate based on the above-described resistance value measurement method. The evaluation results are shown in Table 2.

[Production of liquid crystal display devices]
A polyimide alignment film was provided on the color filter substrate with ITO produced above. An epoxy resin sealant containing spacer particles was printed at a position corresponding to the outer frame of the black matrix provided around the pixel group of the color filter, and the color filter substrate was bonded to the counter substrate. Next, the bonded glass substrate was heat-treated to cure the sealing agent to obtain a laminate of two glass substrates. This glass substrate laminate was degassed under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates to obtain a liquid crystal cell. In the liquid crystal display device, a good image could be obtained without color unevenness.

(Example 2)
In Example 1, when each pattern of K, R, G, and B was formed, post-exposure was performed with 500 mJ / cm ² of light from the resin layer side to the substrate with an ultrahigh pressure mercury lamp before post baking. Except having applied, the board | substrate with ITO was produced by the method similar to Example 1, and was evaluated. Further, when a liquid crystal display device was produced in the same manner as in Example 1, a good image could be obtained.

(Comparative Example 1)
In Example 1, a substrate with ITO was prepared and evaluated in the same manner as in Example 1 except that pattern exposure was performed by the following method when each of K, R, G, and B was formed. did.
As the pattern exposure method, a proximity-type exposure machine (manufactured by Hitachi Deco) having an ultra-high pressure mercury lamp is used, and the exposure mask is set in a state where the substrate and the mask (quartz exposure mask having an image pattern) are vertically set. The distance between the surface and the photosensitive resin layer was set to 200 μm, and the exposure was 70 mJ / cm ² .
Incidentally, when a liquid crystal display device was produced in the same manner as in Example 1, uneven color was found in the image.

(Example 3)
In Example 1, the substrate with ITO was formed in the same manner as in Example 1 except that the temperature in the post-baking process was changed from 220 ° C. to 140 ° C. when forming each pattern of K, R, G, and B. Was made. Moreover, the ITO resistance value was measured by the same method as in Example 1. The results are shown in Table 3.

Example 4
In Example 1, when each pattern of K, R, G, and B was formed, the place where the temperature was raised from room temperature to the temperature (220 ° C.) in the post-baking process over 5 minutes was changed to 2 minutes. A substrate with ITO was produced in the same manner as in Example 1 except that the holding time at temperature was changed from 15 minutes to 18 minutes. Moreover, the ITO resistance value was measured by the same method as in Example 1. The results are shown in Table 3.

(Example 5)
In Example 1, the substrate with ITO was formed in the same manner as in Example 1 except that the temperature in the post-baking process was changed from 220 ° C. to 280 ° C. when forming each pattern of K, R, G, and B. Was made. Moreover, the ITO resistance value was measured by the same method as in Example 1. The results are shown in Table 3.

It is a perspective view which shows the external appearance of the exposure unit which concerns on this invention. It is a perspective view which shows the structure of the scanner of the exposure unit which concerns on this invention. (A) is a top view which shows the exposed area | region formed in a photosensitive material, (B) is a figure which shows the arrangement | sequence of the exposure area by each exposure head. 1 is a perspective view showing a schematic configuration of an exposure head according to the present invention. (A) is sectional drawing of the subscanning direction along the optical axis which shows the structure of the exposure head shown in FIG. 4, (B) is a side view of (A). It is the elements on larger scale which show the structure of a digital micromirror device (DMD). (A) And (B) is explanatory drawing for demonstrating operation | movement of DMD. (A) And (B) is a top view which compares and shows the arrangement | positioning of an exposure beam, and a scanning line by the case where it does not arrange | position inclined DMD and the case where it arranges inclined. (A) is a perspective view which shows the structure of a fiber array light source, (B) is the elements on larger scale of (A), (C) and (D) is a top view which shows the arrangement | sequence of the light emission point in a laser emission part. It is. It is a figure which shows the structure of a multimode optical fiber. It is a top view which shows the structure of a combined laser light source. It is a top view which shows the structure of a laser module. It is a side view which shows the structure of the laser module shown in FIG. It is a partial side view which shows the structure of the laser module shown in FIG. (A) And (B) is sectional drawing which shows the depth of focus in exposure apparatus. (A) And (B) is a figure which shows the example of the use area | region of DMD. (A) is a side view when the use area of DMD is appropriate, (B) is a sectional view in the sub-scanning direction along the optical axis of (A).

Explanation of symbols

50 ... Digital micromirror device (DMD)
54 ... Lens system 66 ... Fiber array light source 166 ... Exposure head

Claims (10)

  A resin layer forming step (a) for providing a photosensitive resin layer comprising a photopolymerizable photosensitive resin composition on a substrate, a pattern exposure step (b) for exposing the photosensitive resin layer with a laser, and the pattern exposure. A pattern for obtaining a color filter pattern through at least a development step (c) for developing the subsequent photosensitive resin layer and a post-baking step (d) for heat-treating the photosensitive resin layer after development. Forming method.   The pattern forming process from the resin layer forming process (a) to the post-baking process (d) is repeated twice or more to provide two or more patterns on the substrate. Pattern formation method.   The pattern formation according to claim 1, further comprising a post-exposure step (e) for exposing the entire surface of the photosensitive resin layer between the development step (c) and the post-bake step (d). Method.   The pattern formation method according to any one of claims 1 to 3, wherein a temperature of the heat treatment in the post-baking step (d) is 180 ° C or higher.   The pattern forming method according to claim 4, wherein the temperature of the heat treatment is 180 to 260 ° C., and the temperature is raised from room temperature to the temperature over 5 to 60 minutes.   6. The pattern forming method according to claim 4, wherein the heating time at the heat treatment temperature is 10 to 300 minutes.   The pattern forming method according to claim 2, wherein at least three colored patterns of red (R), green (G), and blue (B) are provided.   A substrate with a color filter, wherein colored pixels are formed on the substrate by the pattern forming method according to claim 1.   The substrate with a color filter according to claim 8, wherein an ITO transparent electrode is formed.   A display device comprising the substrate with a color filter according to claim 8.

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