JP2009145800A - Method of manufacturing color filter substrate for liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a high quality color filter substrate at low cost for a liquid display device composed of a plurality of patterned layers composed of a first layer of non-photosensitive resin and a photosensitive resin. <P>SOLUTION: In the method of manufacturing the filter substrate for liquid display, the first layer composed of the non-photosensitive resin is formed on a substrate on which a colored layer of a plurality of colors is formed in a pattern, further a second layer containing the photosensitive resin is laminated on the first layer and a pattern processing is performed, and at least the following steps are performed in the described order. (1) a step in which the non-photosensitive resin composition is applied on the substrate and semicured to form the first layer, (2) a step in which the photosensitive resin composition is applied on the first layer and semicured to form the second layer, (3) a step in which the second layer is exposed via a half-tone photo mask, (4) a step in which the second layer is pattern-processed by using a liquid developer to form two kinds or more projections having different heights, and (5) a step in which the first and the second layers are heated to be hardened. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a color filter substrate for a liquid crystal display device comprising a first layer made of a non-photosensitive resin and a second patterned layer made of a photosensitive resin.

  Currently, liquid crystal display devices are used in various applications such as notebook PCs, portable information terminals, desktop monitors, digital cameras, and large liquid crystal televisions, taking advantage of characteristics such as light weight, thinness, and low power consumption. In a portable terminal, visibility regardless of location is regarded as important, and a transflective liquid crystal display device has been developed that enables display in each of transmissive display and reflective display within one pixel. In liquid crystal television applications, characteristics such as high-speed response, wide viewing angle, and high contrast are being improved.

Along with the improvement in performance of liquid crystal display devices, conventional color filters consisting of a light-shielding layer, a colored layer, and a flattening layer, fixed spacers, resin protrusions for liquid crystal alignment control, resin layers for cell gap adjustment, etc. Color filters with additional structures have been developed.
For example, as disclosed in Patent Document 1, in a conventional liquid crystal display device in which bead spacers are dispersed, the orientation of liquid crystal is disturbed around the bead spacers and the contrast is lowered. In the liquid crystal display device in which is formed, the contrast can be improved by forming the fixed spacer in the non-display region.

Further, as disclosed in Non-Patent Document 1, in a vertical alignment mode liquid crystal display device using negative liquid crystal, a resin protrusion for controlling liquid crystal alignment so as to divide the liquid crystal alignment into a plurality of regions. By forming the, it is possible to increase the viewing angle.
Furthermore, in Non-Patent Document 2, in a transflective liquid crystal display device, a transparent resin layer is formed in a reflective display region, and the cell gap of the reflective display region is narrowed, so that the optical path length with the transmissive display region is approximately the same. In addition, a configuration is disclosed in which the reflective display region and the transmissive display region are both bright transflective liquid crystal display devices.
These additional structures are patterned and are usually formed through a photolithography process. Therefore, the color filter provided with the additional structure used in the high-performance liquid crystal display device has a problem that the photolithographic process is increased and the cost is increased as compared with the color filter having a simple configuration.

  As a method for solving these problems, an exposure mask formed of a semi-transmissive film having a UV transmittance control function capable of forming a flattening layer and a fixed spacer of a color filter at once and a light shielding film is disclosed in Patent Document 2. Is disclosed. According to this method, the difference in photocuring of the negative resist is reflected in the film slide by utilizing the difference in ultraviolet transmittance between the semi-transmissive film made of ITO film and the light shielding film made of chromium film or the like. A flattening layer and a fixed spacer of the filter are formed at a time. However, with this method, it has been difficult to maintain the uniformity of the film thickness of the transflective exposed portion having a large amount of film slip, that is, the planarizing layer.

  As a method for forming the fixed spacer and the liquid crystal alignment control resin protrusion by reducing the number of steps, Patent Document 3 discloses a method in which a photomask is exposed a plurality of times while being translated in a predetermined direction. However, this method requires a plurality of exposures, and the exposure time is long, resulting in a decrease in productivity, or exposure pattern misalignment caused by exposure multiple times while shifting a predetermined position. There was a problem that the pattern accuracy deteriorated.

Patent Document 4 describes a method of simultaneously forming a fixed spacer and a resin protrusion for controlling liquid crystal alignment using a halftone mask. In this method, it is possible to form the fixed spacer and the liquid crystal alignment control resin projection by one exposure, and the number of processes can be reduced.
However, although there is no description of the development process in Patent Document 4, in the case of a negative resist, since the halftone exposure part is insufficiently photocured, the half-exposed negative resist is partially dissolved in the developer. There was a problem that part or all of the pattern was peeled off during the development process. Even in the case of a positive resist, if the pattern width of the halftone exposed portion is smaller than 15 μm, there is a problem that a part or all of the pattern is peeled off in the development process.
JP 2001-324716 A JP 2006-184399 A JP 2002-236371 A JP 2007-183589 A Electronic Journal October 1997, page 33 Nikkei Macrodevices separate volume "Flat Panel Display 2003 Practice" 108 pages

  The present invention provides a manufacturing method capable of obtaining a color filter substrate for a liquid crystal display device comprising a first layer made of a non-photosensitive resin and a second patterned layer made of a photosensitive resin at low cost and high quality. The purpose is to provide.

In order to achieve the above object, the present invention comprises the following constitution.
1. A liquid crystal in which a first layer containing a non-photosensitive resin is formed on a substrate on which a plurality of colored layers are patterned, and a second layer containing a photosensitive resin is laminated thereon to perform pattern processing. A method of manufacturing a color filter substrate for a display device,
The manufacturing method of the color filter substrate for liquid crystal display devices characterized by performing at least the following process in this order.
(1) Step of applying and semi-curing a non-photosensitive resin composition on the substrate to form a first layer (2) Applying and semi-curing the photosensitive resin composition onto the first layer (3) Step of exposing the second layer through a halftone photomask (4) Patterning the second layer with a developer to form two or more protrusions having different heights (5) Step of heating and curing the first layer and the second layer 2. The method for producing a color filter substrate for a liquid crystal display device according to 1, wherein the photosensitive resin composition is a resin composition containing at least a polymer, a photopolymerizable monomer, and a photopolymerization initiator.
3. 2. The method for producing a color filter substrate for a liquid crystal display device according to 1, wherein the photosensitive resin composition is a resin composition containing a naphthoquinonediazide compound.
4). The method for producing a color filter substrate for a liquid crystal display device according to any one of claims 1 to 3, wherein the first layer is insoluble or hardly soluble in a developer.
5). The protrusions are (1) a protrusion for controlling the alignment of a vertically aligned liquid crystal display device, (2) a gap adjusting layer for adjusting the thickness of the liquid crystal layer of the liquid crystal display device, or (3) a pair of substrates constituting the liquid crystal display device. The method for producing a color filter substrate for a liquid crystal display device according to any one of items 1 to 4, which is any one or more of fixed spacers for regulating the gap of the liquid crystal display device.
6). The method for producing a color filter substrate for a liquid crystal display device according to any one of 1 to 5, wherein a difference in height between the two or more kinds of protrusions is 0.1 μm or more.

  According to the method for manufacturing a color filter substrate for a liquid crystal display device of the present invention, the planarization layer and the plurality of patterned layers of the color filter for the liquid crystal display device can be collectively processed with high film thickness accuracy, and the high performance of the liquid crystal display device And cost reduction.

  As a result of intensive studies on a method for collectively processing the first layer and the second patterned layer of the color filter for a liquid crystal display device with high film thickness accuracy, the present inventors have found that this is possible by the following method. .

That is, a second layer is formed on a color filter substrate having a plurality of colored layers by applying a first layer composition that is non-photosensitive and hardly soluble or insoluble in a developing solution, and semi-cured. The photosensitive resin composition used for the coating is applied and semi-cured. Subsequently, after exposure through a halftone photomask, the first layer and the plurality of patterned layers can be collectively processed by etching only the second layer with a developer.
The patterned layer formed on the first layer includes (1) a protrusion for controlling the liquid crystal of the vertically aligned liquid crystal, (2) a gap adjusting layer for adjusting the thickness of the liquid crystal layer of the liquid crystal display device, and (3) There is a fixed spacer that regulates a gap between a pair of substrates constituting the liquid crystal display device. Here, (2) “Gap adjustment layer for adjusting the thickness of the liquid crystal layer of the liquid crystal display device” is a liquid crystal cell gap for adjusting the thickness of the liquid crystal formed to be an optimal liquid crystal cell gap for each colored pixel of the color filter. There are an adjustment layer and a gap adjustment layer for adjusting the thickness of the liquid crystal layer in the reflective region in the transflective liquid crystal display. The intended thickness and size of the patterned layer varies depending on the function. The fixed spacer regulates the gap between the pair of substrates constituting the liquid crystal display device. However, in the case of the fixed spacer having a single film thickness, when the liquid crystal cell is pressed with a finger or a pen, the liquid crystal in the pair of substrate gaps The cell gap may be deformed and display unevenness may occur. In order to reduce the deformation amount even when the liquid crystal cell gap is pushed, a sub-fixed spacer lower than the fixed spacer that regulates the liquid crystal cell gap between the pair of substrate gaps can be formed to reduce the deformation amount. Therefore, it is preferable to form a sub-fixed spacer.

Since the fixed spacer is formed such that the liquid crystal cell gap between the pair of substrate gaps is as designed, the height of the fixed spacer is 5 μm or less. The sub-fixed spacer is formed so as to be lower than the fixed spacer, and it is preferable to set the height in the range of 0.1 μm lower to 80% of the fixed spacer in order to reduce the deformation amount of the liquid crystal cell.
The protrusions for controlling the alignment of the vertical alignment liquid crystal can be used even with a single film thickness, but there is a step structure in which the film thickness partially increases at the position where the center of the pixel overlaps the black matrix at the pixel end. Therefore, it is preferable to adjust according to the place where the film thickness of the protrusion is formed. It is preferable to reduce the height of the protrusion for controlling the orientation in a relatively thick part.
The liquid crystal cell is usually formed of a red pixel, a green pixel, and a blue pixel. However, since the light transmitted through each pixel has a different wavelength, the refractive index and the transmittance in the liquid crystal cell are also different. In order to correct the refractive index of light transmitted through each pixel, it is preferable to provide a gap adjustment layer for adjusting the thickness of the liquid crystal layer in each pixel, and the contrast of the liquid crystal cell can be increased. Since it is preferable to reduce the thickness of the liquid crystal layer as the wavelength of transmitted light becomes shorter, it is preferable that the blue liquid crystal cell gap is the narrowest in the blue pixel, and is the green pixel and the red pixel. Therefore, the correction layer for adjusting the thickness of the liquid crystal layer is preferably the thickest blue pixel, and preferably the green pixel and the red pixel, and it is necessary to form a gap adjustment layer for adjusting the thickness of the liquid crystal layer having at least two kinds of heights. .
In the transflective liquid crystal display device, by forming a transparent resin layer in the reflective display area and reducing the thickness of the liquid crystal layer in the reflective display area, the optical path length with the transmissive display area is made approximately the same, the reflective display area, It is preferable that the transmissive display area be a bright transflective liquid crystal display device.
Since the fixing spacer for adjusting the gap between the pair of substrates, the alignment protrusion control object of the vertical alignment liquid crystal, and the liquid crystal layer thickness adjustment layer formed in the reflective display region of the transflective liquid crystal display device have different required film thicknesses, respectively. Although it was processed in separate steps, it would be preferable if these could be processed at the same time, shortening the steps.

  As a method of simultaneously processing a plurality of structures as described above, there is a method of exposing a photosensitive resin through a halftone mask. The halftone mask has a black light shielding film region that shields light to 0.1% or less, a region that transmits light without a light shielding film, and a semi-transmissive light shielding film region that transmits light between 10% and 90%. It is a mask. By exposing through a halftone mask, an exposed area, an area exposed at a low exposure amount, and an unexposed area can be created. The translucent light shielding film region formed on the mask may have one kind of transmittance, but a plurality of transflective light shielding film regions having different transmittances may be formed.

By exposing the photosensitive resin through the halftone mask, the difference in the exposure amount becomes the difference in the solubility in the developing solution, so that a plurality of film thickness structures can be processed. In the case of a negative material, the area that is low-exposed with halftone is thinner than the exposed area, and no pattern is formed on the unexposed area. However, when the exposure amount is small in halftone, there is a problem that the photocuring does not proceed sufficiently and the pattern is lost in the development process.
Conventionally, a photosensitive resin pattern formed with a halftone mask at a low exposure amount has a low height, weak adhesion with a lower layer, and the pattern is easily lost. This tendency is more conspicuous as the film thickness is thicker, the pattern width is narrower and smaller. When the pattern width is 15 μm or less, there is a problem that the pattern is particularly easily lost. As a result of examining the formation of a plurality of structures at the same time while preventing the pattern from being lost, It was confirmed that the developing solution penetrated into the interface with the film. After the step of applying and semi-curing the non-photosensitive resin as the first layer on the substrate, the step of applying and semi-curing the photo-sensitive resin as the second layer is performed, so that the non-photosensitive of the first layer is performed. Since the second photosensitive resin layer is formed and semi-cured in a state where the photosensitive resin layer is not completely thermoset, the adhesion of the first layer to the non-photosensitive resin is improved, and the second layer photosensitive property is improved. It has been discovered that the resin layer can be improved in the development process. By exposing the photosensitive resin through a halftone photomask after this step, it has become possible to form a plurality of complicated structures having a narrow and narrow pattern without omission.
In the case where the second layer is a positive material, the area that is low-exposed with halftone is thinner than the unexposed area, and the exposed area is not patterned. In the case of the positive material, the pattern loss of the halftone-exposed portion is less than that of the negative material. However, in order to form a plurality of complicated structures having a small width and a small pattern without loss, the first material is formed on the substrate. Following the step of applying and semi-curing the non-photosensitive resin as the layer, the step of applying and semi-curing the photosensitive resin as the second layer is preferable.

The first layer made of the non-photosensitive resin composition is preferably a planarization layer having a function of reducing the level difference of the pixels formed on the substrate. In the case where the black matrix formed on the color filter is a resin composition, a step is formed in a portion overlapping the colored pixel material. If this level difference is large, the liquid crystal display device may cause uneven alignment of the liquid crystal and lower the display quality. Therefore, the formation of the first layer prevents the display quality from being reduced when the surface level difference is reduced. .
As a method for measuring the film thickness of the pattern, it can be measured by stylus type surface roughness meter, atomic force microscope, laser microscope, observation of a cross section with a transmission electron microscope, and the like. Although the film thickness difference of the pattern can be measured from the step shape of the measured pattern surface, the film thickness may not be measured from the surface step when the pattern lower layer has irregularities. In this case, the formed pattern is physically cut or scientifically etched to measure the height of the pattern from the substrate surface in a state where the pattern is not substantially formed. It is possible to measure the height difference. When the substrate surface is soft, it is effective to measure the height difference of the pattern from the result of observing the cross section with a transmission electron microscope.

  As a method for obtaining a color filter by photolithography, there are a non-photosensitive polyimide method and a photo-acrylic method, but it is more preferable to apply to a non-photosensitive polyimide method manufacturing apparatus. In the non-photosensitive polyimide method, a non-photosensitive polyimide paste is applied, semi-cured, a positive resist is applied, semi-cured, and exposed, and then the non-photosensitive polyimide and the positive resist are patterned at once with a developer. Thereafter, the positive resist is stripped with a suitable stripping solvent and cured by heating. Thus, in the manufacturing apparatus of the non-photosensitive polyimide method, two coating and semi-cure processes are included in one process, and it is easy to apply the manufacturing method of the present invention.

The semi-cure in the present invention refers to heat treatment at a relatively low temperature mainly for the purpose of volatilization of the solvent component, and specifically refers to heat treatment at 180 ° C. or lower. The temperature of the semi-cure is not particularly limited as long as it is in the above range. However, when the solvent is not sufficiently volatilized, solvent replacement occurs when the second layer is applied, and the underlying first layer swells. Therefore, 100 ° C or higher is preferable. More preferably, it is 130 ° C or higher. The method for performing the semi-cure is not particularly limited as long as the first layer of the base is not affected, and a known method such as a hot plate, a hot air oven, or an IR heater can be used. Similarly, the semi-cure time is not particularly limited, and can be performed in a time of about 1 minute to 90 minutes.
The non-photosensitive layer which is the first layer in the present invention is not particularly limited with respect to the resin component, and epoxy resin, acrylic epoxy resin, acrylic resin, siloxane polymer, polyimide, silicon-containing polyimide, polyimide siloxane, etc. are used. be able to.

The photosensitive resin as the second layer can also be used without particular limitation, and may be a so-called negative photosensitive resin composition containing a polymer, a photopolymerizable monomer, a photopolymerization initiator, and the like. Alternatively, it may be a positive photosensitive resin composition containing a photoacid generator such as a naphthoquinonediazide compound.
The solvent used in the photosensitive resin composition as the second layer is not particularly limited as long as it dissolves the resin component and does not swell and dissolve the non-photosensitive resin layer after semi-curing as a base. be able to.

  For example, ethylene glycol or propylene glycol derivatives such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, propylene glycol monoethyl ether, or propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropionate Aliphatic esters such as 3-methyl-3-methoxybutylacetate, aliphatic alcohols such as ethanol and 3-methyl-3-methoxybutanol, ketones such as cyclopentanone and cyclohexanone, N-methyl- Amide polar solvents such as 2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-va Rorakuton, .gamma.-caprolactone, lactones such as ε- caprolactone can be used. It is preferable to use a single solvent or a mixed solvent of two or more solvents that dissolve these resin components in an appropriate combination. In this case, a poor solvent for the resin to be used can be used as the auxiliary solvent. The preferred solvent is not particularly limited, and examples thereof include a mixed solvent of ethylene glycol or propylene glycol derivative such as propylene glycol monoethyl ether and ketones such as cyclohexanone.

  As a method for applying the first layer and the second layer, a dip method, a roll coating method, a spin coating method, a die coating method, a die coating and spin coating combined method, a wire bar coating method, or the like is preferably used. . After the first layer is applied on the substrate, the solvent is removed by air drying, reduced pressure drying, heat drying, or the like to form a coating film of the second layer. It is more preferable to provide a reduced-pressure drying step before performing semi-cure in an oven or a hot plate, since the coating defects caused by convection are eliminated. Subsequently, an exposure process of photolithography processing is performed. A mask is placed on the coating film of the second layer and selectively exposed to ultraviolet rays using an ultrahigh pressure mercury lamp, a chemical lamp, a high pressure mercury lamp, a laser beam, or the like.

  Although the exposure apparatus is not particularly limited, it is possible to use a proximity exposure machine, a mirror projection exposure machine, a stepper exposure machine, or the like that sets and exposes a photomask within 500 μm on the substrate.

The amount of exposure is not particularly limited, but when expressed by the time integral value of irradiance at 365 nm, the amount of light transmitted through the region where the light-shielding film of the photomask is not formed is preferably 30 to 500 mJ / cm ² .
When the light source is laser light, the exposure amount can be calculated using the center wavelength of the laser light.
The light semi-transmissive region formed in the halftone mask includes a method of forming a film that semi-transmits light, and a method of forming a light semi-transmissive region on average by forming a line or space of 2 μm or less, Either can be used.
In the semi-transmissive light-shielding film region of the halftone mask, a region that transmits 10% to 90% of light is formed. Therefore, when the amount of light transmitted through the region where the light-shielding film is not formed is 300 mJ / cm 2, The amount of light is 30 to 270 mJ / cm 2. The transmittance of the semi-transmissive region is appropriately selected depending on the sensitivity of the photosensitive material and the film thickness to be formed. When the photosensitive material is a negative material, the transmittance of the semi-transmissive region is 10 to 60%. The range is preferably used, and when the photosensitive material is a positive type material, the transmittance of the semi-transmissive region is preferably 40 to 90%.

As the alkali developer, either an organic alkali developer or an inorganic alkali developer can be used. In the inorganic alkaline developer, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is preferably used. In the organic alkali developer, an aqueous amine solution such as an aqueous tetramethylammonium hydroxide solution or methanolamine is preferably used.
The concentration of the alkaline substance in the developer is not particularly limited, but is usually 0.01 to 50% by mass, preferably 0.05 to 5% by mass. Further, a surfactant is also preferably used in the developer, and the pattern shape is improved by adding a nonionic surfactant or the like in an amount of 0.01 to 10% by mass, more preferably 0.1 to 5% by mass. You can also.

In the present invention, the second layer made of the photosensitive resin composition is applied to the first layer made of the non-photosensitive resin composition, and only the photosensitive resin composition is patterned with the developer. One layer must be insoluble or sparingly soluble depending on the developer. If the photosensitive resin composition is immersed in the developer for 3 minutes or more and the film thickness does not change before and after the immersion, it is insoluble in the developer. The fact that the second layer made of the photosensitive resin composition can be patterned and the pattern is not lost means that it is hardly soluble in the developer. When the first layer is dissolved, the pattern of the second layer is lost. Therefore, if the pattern of the second layer is not lost, the first layer is substantially hardly soluble.
Alkali development can be performed by dip development, shower development, paddle development or the like, and these may be combined. After the development, a washing step with pure water or the like may be appropriately added to remove the alkali developer.

The laminated resin layer of the patterned layer obtained from the first layer and the second layer obtained through the development step is then heat-treated. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at a temperature of 180 to 300 ° C, preferably 180 to 260 ° C, continuously or stepwise for 0.25 to 5 hours. Done.
The patterned layer obtained by patterning the second layer is not particularly limited in function, shape, etc., and has various functions, shapes, etc., such as a fixed spacer, a transparent resin layer, and a liquid crystal alignment control protrusion. It can be a thing.

FIG. 1 shows a method of manufacturing a color filter substrate in which a second layer is applied on the first layer of the present invention and exposed with a halftone mask.
Step P1 shows a state in which the first layer 2 is applied on the substrate 1 made of the resin black matrix layer and the colored layer and semi-cured.
Step P2 shows a state where the second layer 3 is applied and semi-cured.
Step P3 shows a state of exposure through the photomask 4. In the photomask 4, a light transmission region 5, a semi-transmission region 6, and a light shielding region 7 are formed. The light 8 in the exposure is irradiated to the second layer through the light transmission region 5 and the semi-transmission region 6 of the photomask.
Step P4 shows a state in which the second layer is developed. The second layer pattern 9 corresponding to the transmissive region of the photomask is formed with a thicker pattern than the second layer pattern 10 corresponding to the semi-transmissive region of the photomask.

Example 1
A. Preparation of black paste 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane were mixed with N-methyl-2-pyrrolidone. It was made to react as a solvent and the polyimide precursor (polyamic acid) solution was obtained.

A carbon black mill base having the following composition was dispersed using a homogenizer at 7000 rpm for 30 minutes, and glass beads were filtered to prepare a black paste.
Carbon black mill-based composition carbon black (MA100, manufactured by Mitsubishi Kasei Co., Ltd.): 4.6 parts polyimide precursor solution: 24.0 parts N-methylpyrrolidone: 61.4 parts Glass beads: 90.0 parts.
B. Synthesis of Polymer Dispersant 161.3 g of 4,4′-diaminobenzanilide, 176.7 g of 3,3′-diaminodiphenylsulfone, and 18.6 g of bis (3-aminopropyl) tetramethyldisiloxane were obtained in 2667 g of γ-butyrolactone, Charged together with 527 g of N-methyl-2-pyrrolidone, added 439.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, reacted at 70 ° C. for 3 hours, and then phthalic anhydride. 2 g was added, and the mixture was further reacted at 70 ° C. for 2 hours to obtain a polymer dispersant (PD) which was a 20 wt% polyamic acid solution.
C. Preparation of Color Paste Pigment Red PR254, 3.87 g (86 wt%), Pigment Red PR122, 0.63 g (14 wt%), Polymer Dispersant (PD) 22.5 g and γ-butyrolactone 42.8 g, 3-methoxy-3 -20.2 g of methyl-1-butanol was charged together with 90 g of glass beads, and after dispersing for 5 hours at 7000 rpm using a homogenizer, the glass beads were filtered and removed. A red dispersion 5% solution (GD) was thus obtained.
A solution obtained by diluting 8.0 g of polyamic acid solution (PAA) with 42.0 g of γ-butyrolactone was added to and mixed with 50.0 g of dispersion (GD) to obtain a red color paste (R-1). Similarly, green paste (G-1) and blue paste (B-1) were obtained at the ratios shown in Table 1.

D. Preparation of resin black matrix The black paste was applied to a glass substrate (Corning, Eagle XG material) with a slit coater, and heated for 10 minutes on a 130 ° C. hot plate to form a semi-cured black resin coating film. . A positive photoresist (Rohm and Haas Electronic Materials, "LC-100A") is applied with a slit coater so that the film thickness after pre-baking is 1.0 μm, and dried on a hot plate at 100 ° C. for 5 minutes. , Semi-cure.
Using a UV exposure apparatus PLA-501F manufactured by Canon Inc., exposure was performed at 100 mJ / cm ² (ultraviolet intensity of 365 nm) through a photomask, and mask exposure was performed so that the width of the black matrix became 8 μm at a pitch of 48 μm. Next, using 2.25% tetramethylammonium hydroxide aqueous solution, photoresist development and resin coating etching were simultaneously performed to form a pattern, and the resist was peeled off with methyl cellosolve acetate. Next, it was imidized by heat treatment for 15 minutes on a 300 ° C. hot plate to form a black matrix layer. The formed black matrix had a thickness of 1.6 μm.
A red paste (R-) containing a non-photosensitive resin so that the chromaticity (x, y) when passing through a C light source on a glass substrate on which a black matrix is patterned is (0.464, 0.282). 1) was coated on a glass substrate with a spinner. The coating film was dried in an oven at 120 ° C. for 20 minutes and semi-cured. A positive photoresist (“LC-100A”) was applied thereon to a thickness of 1 μm after drying, dried in an oven at 90 ° C. for 10 minutes, and semi-cured. Using a UV exposure machine PLA-501F manufactured by Canon Inc., exposure was performed at 100 mJ / cm ² (ultraviolet intensity of 365 nm) through a photomask. After the exposure, the film was immersed in a developer at 23 ° C. composed of a 2.0% aqueous solution of tetramethylammonium hydroxide, and the development of the photoresist and the etching of the colored coating film of polyamic acid were simultaneously performed. The photoresist that became unnecessary after etching was stripped with methyl cellosolve acetate. Furthermore, the colored coating film of polyamic acid was heat-treated in an oven at 240 ° C. for 30 minutes and imidized to form a red pixel.
Next, a blue paste (B-1) containing a non-photosensitive resin is applied so that the finished chromaticity (x, y) when passing through the C light source is (0.152, 0.190). It was dried in a 120 ° C. oven for 20 minutes and semi-cured. A positive photoresist (“LC-100A”) was applied thereon to a thickness of 1 μm after drying, dried in an oven at 90 ° C. for 10 minutes, and semi-cured. Using a UV exposure machine PLA-501F manufactured by Canon Inc., exposure was performed at 100 mJ / cm ² (ultraviolet intensity of 365 nm) through a photomask. After the exposure, the film was immersed in a developer at 23 ° C. composed of a 2.0% aqueous solution of tetramethylammonium hydroxide, and the development of the photoresist and the etching of the colored coating film of polyamic acid were simultaneously performed. The photoresist that became unnecessary after etching was stripped with methyl cellosolve acetate. Furthermore, the colored coating film of polyamic acid was heat-treated in an oven at 240 ° C. for 30 minutes and imidized to form blue pixels.
Next, a green paste (G-1) containing a non-photosensitive resin was applied so that the finished chromaticity (x, y) when passing through a C light source would be (0.284, 0.443), and 120 ° C. Were dried in an oven for 20 minutes and semi-cured. A positive photoresist (“LC-100A”) was applied thereon to a thickness of 1 μm after drying, dried in an oven at 90 ° C. for 10 minutes, and semi-cured. Using a UV exposure machine PLA-501F manufactured by Canon Inc., exposure was performed at 100 mJ / cm ² (ultraviolet intensity of 365 nm) through a photomask. After the exposure, the film was immersed in a developer at 23 ° C. composed of a 2.0% aqueous solution of tetramethylammonium hydroxide, and the development of the photoresist and the etching of the colored coating film of polyamic acid were simultaneously performed. The photoresist that became unnecessary after etching was stripped with methyl cellosolve acetate. Furthermore, the colored coating film of polyamic acid was heat-treated in an oven at 240 ° C. for 30 minutes to imidize to form a green pixel.
The color filter pixel was formed on the substrate by the above process.

[Preparation of non-photosensitive resin composition (for first layer)]
After dissolving 65.05 g of trimellitic acid in 280 g of γ-butyrolactone, 74.95 g of γ-aminopropyltriethoxysilane was added and heated at 120 ° C. for 2 hours. To 20 g of the resulting solution, 7 g of bisphenoxyethanol fluorenediglycidyl ether and 15 g of diethylene glycol dimethyl ether are added and stirred at room temperature (about 23 ° C.) for 2 hours to obtain a non-photosensitive resin solution composition for the first layer. It was.

[Application of first layer, semi-cure]
The obtained non-photosensitive resin solution composition for a color filter is spin-coated on a substrate on which color filter pixels are formed so that the thickness after this curing is 1.5 μm and heated in an oven at 130 ° C. for 10 minutes. Thus, a semi-cured non-photosensitive resin composition coating film was obtained.
[Preparation of photosensitive resin composition (for second layer, fixed spacer)]
70.0 g of acrylic copolymer solution (Daicel Chemical Industries, Ltd., Cyclomer P, ACA-250, 43 mass% solution), 30.0 g of dipentaerythritol hexaacrylate as a polyfunctional monomer, and 2-meryl as a photopolymerization initiator −1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one was added in an amount of 10.0 g, and cyclopentanone 217.5 g was added as a solvent, and the acrylic resin concentration (total concentration of acrylic copolymer and monomer) was added. ) 20% by mass of the second layer photosensitive transparent resin composition (A) was obtained.

[Second layer coating, semi-cure]
The second layer (A) is spin-coated on the color filter substrate obtained by applying and semi-curing the non-photosensitive resin solution composition so that the film thickness after the main curing is 3.0 μm. Semi-cure treatment was carried out by heating in an oven at 5 ° C. for 5 minutes. A laminated coating film of a first layer comprising a non-photosensitive resin composition and a second layer comprising a photosensitive resin composition (A) was obtained.

[Batch formation of fixed spacers different in film thickness from the first layer]
Using a UV exposure machine PLA-501F manufactured by Canon Inc., through a halftone photomask pattern having a light transmissive region for forming a fixed spacer and a light semi-transmissive region having a transmittance of 50% for forming a sub-fixed spacer on the photomask. And 120 mJ / cm ² (ultraviolet intensity of 365 nm). After exposure, the film was developed by immersing in a developer composed of a 0.5% aqueous solution of tetramethylammonium hydroxide for 90 seconds. Heat treatment was performed at 230 ° C. for 30 minutes in a hot air oven to form fixed spacers having different heights composed of the second layer on the first layer having a thickness of 1.5 μm. Two types of fixed spacers having a film thickness of 3.0 μm and a diameter of 15 μm and sub-fixing spacers having a film thickness of 2.8 μm and a diameter of 12 μm could be formed at once.
Example 2
[Collective formation of protrusions for controlling liquid crystal alignment different in film thickness from the first layer]
A positive-type photosensitive resist (“LC-100A”) is applied to a color filter substrate obtained by applying and semi-curing the first layer produced in the same manner as in Example 1, and the thickness after this cure is 1 It was applied to a thickness of 5 μm, dried in an oven at 90 ° C. for 10 minutes, and semi-cured. A laminated coating film of a first layer made of a non-photosensitive resin composition and a second layer made of a positive resist was obtained.

Subsequently, using a UV exposure machine PLA-501F manufactured by Canon Inc., a light shielding film for forming alignment control protrusions on a photomask and light having a transmittance of 50% for forming alignment control protrusions formed on a single pixel portion. Exposure was performed at 150 mJ / cm ² (ultraviolet intensity of 365 nm) through a halftone photomask pattern having a semi-transmissive region. After the exposure, the film was developed by being immersed in a developer composed of a 2.2% aqueous solution of tetramethylammonium hydroxide. A heat treatment was performed at 230 ° C. for 30 minutes to form a liquid crystal alignment control protrusion composed of the second layer on the first layer having a thickness of 1.5 μm. The liquid crystal alignment control protrusions were able to be formed in a batch of two types: a stripe shape with a film thickness of 1.5 μm and a width of 12 μm and a stripe shape with a film thickness of 1.2 μm and a width of 10 μm.

Example 3
[Preparation of photosensitive resin composition (for second layer, liquid crystal cell gap adjustment layer)]
70.0 g of acrylic copolymer solution (Daicel Chemical Industries, Ltd., Cyclomer P, ACA-250, 43 mass% solution), 30.0 g of dipentaerythritol hexaacrylate as a polyfunctional monomer, and 2-meryl as a photopolymerization initiator 10.0 g of -1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one and 2- (2H-benzotriazol-2-yl) -4- (1,1, 3 g of 3,3-tetramethylbutyl) phenol and 217.5 g of cyclopentanone as a solvent were added, and a photosensitive transparent resin composition (B) having an acrylic resin concentration (total concentration of acrylic copolymer and monomer) of 20% by mass. Got.

[Batch formation of liquid crystal cell gap adjusting layer having a film thickness different from that of the first layer]
The color filter substrate obtained by applying and semi-curing the first layer produced in the same manner as in Example 1 is coated with the photosensitive transparent resin composition (B) as the second layer. A resin comprising a first layer and a second layer (B) made of a non-photosensitive resin composition that has been subjected to a semi-cure treatment by spin coating to a thickness of 0.4 μm and heating in an oven at 90 ° C. for 5 minutes A layered coating film was obtained.

Subsequently, using a UV exposure apparatus PLA-501F manufactured by Canon Inc., a light-shielding film on the red pixel, a light-shielding film having a transmittance of 10% on the green pixel, and a light transmissive region on the blue pixel. The film was exposed to 100 mJ / cm ² (ultraviolet intensity of 365 nm) through a tone photomask pattern. After the exposure, the film was immersed in a developer composed of a 0.5% aqueous solution of tetramethylammonium hydroxide and developed. A heat treatment was performed at 230 ° C. for 30 minutes to form a liquid crystal cell gap adjusting layer composed of the second layer on the first layer having a thickness of 1.5 μm. The liquid crystal cell gap adjustment layer had a film thickness of 0.4 μm on the blue pixel, a film thickness of 0.2 μm on the green pixel, and no liquid crystal cell gap adjustment layer was formed on the red pixel. Liquid crystal cell gap adjusting layers having different film thicknesses could be formed at once.
Example 4
[Batch formation of first layer, fixed spacer, and protrusion for controlling liquid crystal alignment]
A positive photosensitive resist (“LC-100A”) is applied to the color filter substrate obtained by applying and semi-curing the first layer produced in the same manner as in Example 1, and the film thickness after this cure is 2 The laminated coating film of the 1st layer which consists of the non-photosensitive resin composition which apply | coated so that it might be set to 0.0 micrometer, and was dried for 10 minutes in 90 degreeC oven, and the positive resist was obtained. .

Subsequently, using a UV exposure apparatus PLA-501F manufactured by Canon Inc., a half-tone photo having a light-shielding film for forming a fixed spacer on a photomask and a light semi-transmissive region having a transmittance of 90% for forming an orientation control protrusion. It exposed with the exposure amount of the photomask transmissive area | region through a mask pattern at 100 mJ / cm < ² > (365 nm ultraviolet intensity). After the exposure, the film was immersed in a developer composed of a 2.2% aqueous solution of tetramethylammonium hydroxide and developed. A heat treatment was performed at 230 ° C. for 30 minutes to form a fixed spacer made of the second layer and a liquid crystal alignment control protrusion on the first layer having a thickness of 1.5 μm. The fixed spacer has a thickness of 2.0 μm and a diameter of 12 μm, the liquid crystal alignment control protrusion has a stripe shape of a film thickness of 1.2 μm and a width of 10 μm, and the fixed spacer and the liquid crystal alignment control protrusion have two types at once. Could be formed.
Example 5
[Batch formation of first layer, fixed spacer, and transflective liquid crystal cell gap adjustment layer]
The second layer of the photosensitive transparent resin composition (A) is applied to the color filter substrate obtained by applying and semi-curing the first layer produced in the same manner as in Example 1, and the film thickness after this curing is thick. Spin coating to a thickness of 3.0 μm and heating in an oven at 90 ° C. for 5 minutes to obtain a laminated coating film of a first layer and a second layer made of a semi-cured non-photosensitive resin composition It was.

Subsequently, using a UV exposure apparatus PLA-501F manufactured by Canon Inc., a halftone photomask pattern having a light transmission region for forming a fixed spacer and a semi-transmission region having a transmittance of 20% for forming a liquid crystal cell gap adjustment layer is formed. To 300 mJ / cm 2 (ultraviolet intensity of 365 nm). After the exposure, the film was immersed in a developer composed of a 0.5% aqueous solution of tetramethylammonium hydroxide and developed. Heat treatment was performed at 230 ° C. for 30 minutes, and a fixed spacer and a liquid crystal cell gap adjustment layer made of the second layer were formed on the first layer having a thickness of 1.5 μm. The fixed spacer has a film thickness of 3.0 μm and a diameter of 15 μm, and the transflective liquid crystal cell gap adjustment layer has a film thickness of 1.5 μm and a width of 30 μm, and has a stripe shape. The types could be formed at once.
Example 6
[Batch formation of first layer, transflective liquid crystal cell gap adjusting layer, and liquid crystal alignment control protrusion]
The color filter substrate obtained by applying and semi-curing the first layer produced in the same manner as in Example 1 is coated with the photosensitive transparent resin composition (B) as the second layer. Spin coating to a thickness of 1.5 μm and heating in an oven at 90 ° C. for 5 minutes to obtain a laminated coating film of a first layer and a second layer made of a semi-cured non-photosensitive resin composition It was.

Subsequently, using a UV exposure machine PLA-501F manufactured by Canon Inc., a halftone in which a light transmission region for a liquid crystal cell gap adjustment layer shape and a semi-transmission film having a transmittance of 60% for forming a liquid crystal alignment control protrusion are formed. It exposed to 150 mJ / cm < ² > (365 nm ultraviolet intensity) through the photomask pattern. After the exposure, the film was immersed in a developer composed of a 0.5% aqueous solution of tetramethylammonium hydroxide and developed. A heat treatment was performed at 230 ° C. for 30 minutes to form a liquid crystal cell gap adjusting layer composed of the second layer and a liquid crystal alignment control protrusion on the first layer having a thickness of 1.5 μm. The liquid crystal cell gap adjustment layer is formed in a stripe shape with a film thickness of 1.5 μm and a width of 30 μm, and the liquid crystal alignment control protrusion has a film thickness of 1.2 μm, a width of 12 μm, a liquid crystal cell gap adjustment layer, and a liquid crystal alignment control protrusion. The types could be formed at once.
Example 7
[Batch formation of first layer, fixed spacer, transflective liquid crystal cell gap adjusting layer, and liquid crystal alignment control protrusion]
The color filter substrate obtained by applying and semi-curing the first layer produced in the same manner as in Example 1 is coated with the photosensitive transparent resin composition (A) as the second layer. Spin coating to a thickness of 3.0 μm and heating in an oven at 90 ° C. for 5 minutes to obtain a laminated coating film of a first layer and a second layer made of a semi-cured non-photosensitive resin composition It was.

Subsequently, using a UV exposure machine PLA-501F manufactured by Canon Inc., a light transmissive region is formed for forming a fixed spacer, a semi-transmissive film having a transmittance of 20% is formed for forming a liquid crystal cell gap adjusting layer for semi-transmissive, For alignment control projection formation, exposure was performed at 400 mJ / cm ² (ultraviolet intensity of 365 nm) through a halftone photomask pattern on which a transflective film having a transmittance of 10% was formed. After the exposure, the film was immersed in a developer composed of a 0.5% aqueous solution of tetramethylammonium hydroxide and developed. A heat treatment was performed at 230 ° C. for 30 minutes, and a fixed spacer, a liquid crystal cell gap adjusting layer, and a liquid crystal alignment control protrusion made of the second layer were collectively formed on the first layer having a thickness of 1.5 μm. The fixed spacer is formed with a thickness of 3.0 μm and a diameter of 15 μm, the liquid crystal cell gap adjustment layer is formed in a stripe shape with a thickness of 1.5 μm and a width of 30 μm, and the liquid crystal alignment control protrusion has a thickness of 1.2 μm and a width. It was formed in a stripe shape with a thickness of 12 μm. Three types of fixed spacer, liquid crystal cell gap adjusting layer for semi-transmission, and liquid crystal alignment control protrusion could be formed at a time.

Comparative Example 1
[Batch formation of first layer and fixed spacer]
In the same manner as in Example 1, the non-photosensitive resin solution composition was spin-coated so that the film thickness after this curing was 1.5 μm, heated in an oven at 130 ° C. for 5 minutes, and then in an oven at 230 ° C. for 30 minutes. By heating, a color filter substrate on which a planarizing layer was formed was obtained. The obtained color filter substrate was irradiated with ultraviolet rays and immersed in an alkaline cleaning solution, and then rinsed with pure water and dried with an air knife and washed.
The washed color filter substrate was spin-coated with the photosensitive transparent resin composition (A) so that the film thickness after the main curing was 3.0 μm, and heated in an oven at 90 ° C. for 5 minutes.

Using a UV exposure machine PLA-501F manufactured by Canon Inc., through a halftone photomask pattern having a light transmissive region for forming a fixed spacer and a light semi-transmissive region having a transmittance of 50% for forming a sub-fixed spacer on the photomask. 120 mJ / cm ² (ultraviolet intensity of 365 nm). After exposure, the film was developed by immersing in a developer composed of a 0.5% aqueous solution of tetramethylammonium hydroxide for 90 seconds. Heat treatment was performed in an oven at 230 ° C. for 30 minutes to form a fixed spacer. Although a fixed spacer having a film thickness of 3.0 μm and a diameter of 18 μm could be formed, the sub-fixed spacer having a smaller film thickness and a smaller diameter than the fixed spacer could not be formed by being peeled off during the development process.

It is a figure which shows the process of the manufacturing method of the color filter substrate of this invention.

Explanation of symbols

1: Substrate 2: First layer 3: Second layer 4: Photomask 5: Light transmission region 6: Transflective region 7: Light shielding region 8: Light in exposure 9: First corresponding to the transmission region of the photomask 2 layer pattern 10: second layer pattern corresponding to the transflective region of the photomask

Claims (6)

A liquid crystal in which a first layer containing a non-photosensitive resin is formed on a substrate on which a plurality of colored layers are patterned, and a second layer containing a photosensitive resin is laminated thereon to perform pattern processing. A method of manufacturing a color filter substrate for a display device,
The manufacturing method of the color filter substrate for liquid crystal display devices characterized by performing at least the following process in this order.
(1) Step of applying and semi-curing a non-photosensitive resin composition on the substrate to form a first layer (2) Applying and semi-curing a photosensitive resin composition on the first layer to form a second layer (3) Step of exposing the second layer through a halftone photomask (4) Two or more kinds of protrusions having different heights by patterning the second layer with a developer (5) A step of heating and curing the first layer and the second layer The method for producing a color filter substrate for a liquid crystal display device according to claim 1, wherein the photosensitive resin composition is a resin composition containing at least a polymer, a photopolymerizable monomer, and a photopolymerization initiator. The method for producing a color filter substrate for a liquid crystal display device according to claim 1, wherein the photosensitive resin composition is a resin composition containing a naphthoquinonediazide compound. The method for producing a color filter substrate for a liquid crystal display device according to claim 1, wherein the first layer is insoluble or hardly soluble in a developer. The protrusions are (1) a protrusion for controlling the alignment of a vertically aligned liquid crystal display device, (2) a gap adjusting layer for adjusting the thickness of the liquid crystal layer of the liquid crystal display device, or (3) a pair of substrates constituting the liquid crystal display device. The method for producing a color filter substrate for a liquid crystal display device according to any one of claims 1 to 4, wherein the spacer is one or more of fixed spacers that regulate the gap of the liquid crystal display device. The method for producing a color filter substrate for a liquid crystal display device according to claim 1, wherein a difference in height between the two or more kinds of protrusions is 0.1 μm or more.

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