JP2017187537A - Color filter substrate and liquid crystal display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter substrate having a structure that allows manufacturing with less manufacturing processes than a conventional one, and also to provide a liquid crystal display device using the same.SOLUTION: A color filter substrate includes a black matrix, part of which forms a protrusion of a spacer holding a cell gap between the color filter substrate and a TFT array substrate. The spacer preferably includes two or more types of spacers having different heights. A liquid crystal display device uses the color filter substrate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a color filter substrate for a liquid crystal display device and a liquid crystal display device using the same.

  A liquid crystal display device is a liquid crystal in which a TFT array substrate on which a thin film transistor (TFT) switching element is formed on a glass substrate and a color filter substrate are arranged to face each other with a predetermined interval, and these substrates are bonded together by a sealing material Consists of panels. A color filter is a member necessary for color display of a liquid crystal display device, and a colored layer of red pixels, green pixels, and blue pixels is finely patterned between a grid-like black matrix formed on a glass substrate. The structure is common. (Hereinafter, the black matrix is abbreviated as BM).

  In order to maintain a cell gap between the color filter substrate and the TFT array substrate, a method of forming a spacer by patterning a transparent resin on the color filter is generally used, but the cross-sectional area of the spacer portion in the liquid crystal panel is small. In the panel assembly process, the cell gap between the substrates is difficult to be uniform, and the liquid crystal display device is liable to cause color unevenness. Further, even when an excessive load is locally applied, color unevenness or the like is likely to occur in the liquid crystal display device.

  Conversely, if the spacer cross-sectional area is large, the cell gap between the substrates will be uniform during the panel assembly process, but the cell gap does not follow when heat shrinks during firing of the sealing material, and vacuum bubbles are generated in the liquid crystal cell. It becomes easy to do.

  As a method for solving these problems, Patent Document 1 discloses a method of forming a spacer (sub-spacer) having a height lower than that of a spacer (main spacer) that holds a cell gap between substrates.

  On the other hand, in recent high-definition liquid crystal display devices, there is a problem of perspective color mixture that appears white when light leaked from adjacent pixels is mixed when viewed obliquely. In order to improve this perspective color mixture, a BOC (BM on Color) configuration is proposed in which a BM is formed after a colored layer of red pixels, green pixels, and blue pixels is formed on a glass substrate.

  FIG. 6 shows a schematic cross-sectional view of a conventional color filter substrate in which a colored layer is formed after BM is formed, and FIG. 7 shows a BOC configuration color filter substrate in which BM is formed after forming a colored layer.

Japanese Patent No. 3925142

  In order to form main spacers and sub-spacers having different heights, a plurality of exposure processes are performed by changing the exposure amount, or a plurality of exposure processes are performed using a plurality of photomasks having different transmittances. Alternatively, there is a method of using a gradation mask having light transmitting portions having different transmittances, but each of them requires a process only for forming a spacer, and there is a problem that the number of exposure processes increases.

  The present invention has been made in view of the above-mentioned problems, and the object of the present invention is a structure that can be manufactured with fewer steps than before in a BOC-structured color filter substrate in which a BM is formed after forming a colored layer. And a liquid crystal display device using the color filter substrate.

In order to solve the above-described problem, the invention described in claim 1 is used in a liquid crystal display device, and includes a color layer, a black matrix, and a spacer that holds a cell gap between the TFT array substrate. In the substrate,
The color filter substrate is characterized in that a part of the black matrix forms a convex portion of the spacer.

  The invention according to claim 2 is the color filter substrate according to claim 1, wherein the spacer is two or more kinds of spacers having different heights.

  According to a third aspect of the present invention, at least the lower part of the lowest spacer among the two or more types of spacers having different heights is present at a boundary portion of different colored layers with a width of 1 to 5 μm in a sectional view. The color filter substrate according to claim 2.

  According to a fourth aspect of the present invention, a boundary portion of different colored layers exists below at least the highest spacer among the two or more types of spacers having different heights, and one colored layer is present at the boundary portion. 3. A color filter substrate according to claim 2, wherein convex portions are formed.

  The invention according to claim 5 is characterized in that, among the two or more kinds of spacers having different heights, different colored layers are laminated under at least the highest spacer. This is a color filter substrate.

  The invention according to claim 6 is characterized in that a difference in height between the highest spacer and the lowest spacer among the two or more kinds of spacers having different heights is 0.3 to 0.7 μm. The color filter substrate according to any one of claims 1 to 5.

  The invention according to claim 7 is a liquid crystal display device comprising the color filter substrate according to any one of claims 1 to 6.

  According to the structure of the color filter substrate of the present invention, in the BOC configuration in which the BM is formed after the colored layer is formed, a part of the BM forms the convex portion of the spacer. This can be performed in the same exposure process, and can contribute to the improvement of the productivity and manufacturing cost of the color filter substrate and the liquid crystal display device using the same.

It is a schematic cross section which shows 1st Embodiment based on the color filter substrate of this invention. It is a schematic cross section which shows the modification of 1st Embodiment based on the color filter substrate of this invention. It is a schematic cross section which shows 2nd Embodiment based on the color filter substrate of this invention. It is a schematic cross section which shows a part of manufacturing process based on 1st Embodiment of the color filter substrate of this invention. It is a schematic cross section which shows a part of manufacturing process based on 2nd Embodiment of the color filter substrate of this invention. It is a schematic cross section showing a conventional color filter substrate. It is a schematic cross section which shows the color filter substrate of the conventional BOC structure.

  Hereinafter, embodiments of the color filter substrate of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments without departing from the spirit of the present invention. In addition, the same code | symbol is attached | subjected about the same component unless there is a reason for convenience, and the overlapping description is abbreviate | omitted. Further, in the drawings used in the following description, in order to make the features easier to understand, the portions that become the features are enlarged and shown, and the dimensional ratios of the respective constituent elements are not the same as actual.

  FIG. 1 is a schematic cross-sectional view showing a first embodiment of a color filter substrate of the present invention. Here, red, blue, and green colored layers 2 (R), 2 (B), and 2 (G) are formed on the transparent substrate 1 to form a BOC-structured BM (4a). Furthermore, two types of spacers (main spacer 6c-1 and sub-spacer 6b-1) having different heights are formed, but depending on the purpose and application of the liquid crystal display device, one type of spacer having the same height may be used. Three or more different heights may be used.

  Further, an overcoat layer 5 is formed on the entire surface as a protective film. Therefore, the main spacer 6c-1 and the sub spacer 6b-1 are overcoated with the main spacer resist pattern 4c-1 and the sub spacer resist pattern 4b-1, respectively. A coat layer 5 is used.

  Further, the color filter substrate of the present invention is characterized in that a part of the BM is a main spacer resist pattern 4c-1 and a sub-spacer resist pattern 4b-1 that form a convex portion of the spacer. This is because the main spacer resist pattern 4c-1, the sub spacer resist pattern 4b-1, and the BM (4a) are produced in the same exposure process. The resist pattern 4b-1 and BM (4a) are made of the same resist composition (hereinafter abbreviated as resist).

  In the first embodiment of the color filter substrate of the present invention, as shown in FIG. 1, the sub-spacer resist pattern 4b-1 that forms the convex portion of the sub-spacer 6b-1 having a low height is formed of different colored layers. The boundary portion has a portion having a width of 1 to 5 μm smaller than the width of the BM in a cross-sectional view. (The reason why the width is smaller than the width of the BM will be described in the part relating to the manufacturing process described later).

  Further, in the first embodiment of the color filter substrate of the present invention, as shown in FIG. 1, the main spacer resist pattern 4c-1 that forms the convex portion of the higher main spacer 6c-1 is colored differently. There is a boundary between layers, and one colored layer forms a convex portion at the boundary. (The reason for forming the convex portion will be described in the part relating to the manufacturing process described later).

  FIG. 2 is a schematic cross-sectional view showing a modification of the first embodiment of the color filter substrate of the present invention. The difference from FIG. 1 is the shape of the portion of the sub-spacer resist pattern 4b-1 that forms the convex portion of the sub-spacer 6b-1, which exists at the boundary between different colored layers. FIG. In contrast, the modification of FIG. 2 has a rectangular shape. Even if it is a rectangular shape, it is the same as the case of the inverted trapezoidal shape of FIG.

  In FIG. 1B, the shape of the portion existing at the boundary between the different colored layers is an inverted trapezoidal shape or a rectangular shape, but even if the lower side is an inverted triangular shape that does not reach the transparent substrate 1. Good. These shapes are made according to the purpose and application of the liquid crystal display device and depend on the type and height of the spacer and the resist characteristics.

  FIG. 3 is a schematic cross-sectional view showing a second embodiment of the color filter substrate of the present invention. Here, the sub-spacer 6b-2 and the sub-spacer resist pattern 4b-2 forming the convex portion are the same as the main spacer 6c-1 and the main spacer resist pattern 4c-1 forming the convex portion in FIG. The boundary portion of the different colored layer exists under the resist pattern 4b-2 for the sub-spacer, and one colored layer forms a convex portion at the boundary portion.

  On the other hand, in the second embodiment, as shown in FIG. 3, in the region serving as the base of the main spacer 6 c-2 under the main spacer resist pattern 4 c-2 that forms the convex portion of the higher main spacer 6 c-2. Are stacked with different colored layers. By laminating, the colored layer becomes higher (thick), and the height of the main spacer 6c-2 can be made higher than that of the sub-spacer 6b-2.

  In the color filter substrate of the present invention, it is necessary for the spacer that the difference in height between the highest spacer and the lowest spacer among the two or more kinds of spacers having different heights is 0.3 to 0.7 μm. From the viewpoint of mechanical characteristics.

  Hereinafter, the manufacturing process for producing the structure of the color filter substrate of the present invention will be described.

  FIG. 4 is a schematic cross-sectional view showing a part of the manufacturing process for producing the first embodiment (FIG. 1) of the color filter substrate of the present invention. FIG. 4A shows a state where the colored layers 2 (R), 2 (B), and 2 (G) are formed on the transparent substrate 1. What is characteristic here is that the BM space portion 2a that functions only as a BM, the subspacer space portion 2b-1 that functions as a subspace in addition to the BM, and the main spacer coloring layer projection that functions as a main space in addition to the BM. That is, the part 2c-1 exists.

  The space part 2b-1 for subspacers is in the position which forms the subspacer of the boundary part of a different colored layer, and has a width | variety of 1-5 micrometers smaller than the width | variety of the space part 2a for BM by sectional view. Accordingly, the volume of the sub-spacer space 2b-1 is smaller than that of the BM space 2a. The convex shape of the colored layer convex portion 2c-1 for the main spacer is formed by forming the pattern of the colored layer 2 (R), and then applying the colored layer 2 (B) to color the end face of the colored layer 2 (R). The colored layer 2 (B) is formed by patterning so that the end face of the layer 2 (B) remains on the surface.

  FIG. 4B shows a state in which a resist 3 for forming BM and spacers is applied on the configuration of FIG. Here, as described above, the presence of the BM space portion 2a, the sub-spacer space portion 2b-1, and the main spacer colored layer convex portion 2c-1 causes a difference in height on the surface of the resist 3. . That is, 3c-1 on the coloring layer convex part 2c-1 for the main spacer is the highest, and then the volume of the subspacer space part 2b-1 is smaller than the volume of the BM space part 2a. The height is 3b-1 on the space 2b-1 and 3a on the BM space 2a.

  FIG. 4C shows a state in which the pattern of BM (4a), the sub-spacer resist pattern 4b-1, and the main spacer resist pattern 4c-1 are formed by performing exposure and development in the form of FIG. 4B. Show. Here, the photomask used for exposure has the above-described height difference on the surface of the resist 3, and thus may be a photomask having a constant transmittance. However, the BM (4a) pattern and sub-spacer can be more reliably used. In order to match the height of the resist pattern 4b-1 for main and the resist pattern 4c-1 for main spacer to the target, it is preferable to use a gradation mask having light transmitting portions having different transmittances. In any case, the BM and the spacer can be formed in the same process.

  FIG. 4D shows a form in which the overcoat layer 5 is laminated on the form of FIG. By using a transparent resin for the overcoat layer, the insulating property of the spacer portion can be preferably increased. Thus, the main spacer 6c-1 and the sub-spacer 6b-1 are entirely formed, and the first embodiment (FIG. 1) of the color filter substrate of the present invention is manufactured.

  FIG. 5 is a schematic cross-sectional view showing a part of the manufacturing process for producing the second embodiment (FIG. 3) of the color filter substrate of the present invention. FIG. 5A shows a state where the colored layers 2 (R), 2 (B), and 2 (G) are formed on the transparent substrate 1. What is characteristic here is the BM space 2a that functions only as a BM, the sub-spacer coloring layer projection 2b-2 that functions as a subspace in addition to the BM, and the coloring for the main spacer that functions as a main space in addition to the BM. That is, the layer stacking portion 2c-2 exists.

  The convex shape of the colored layer convex portion 2b-2 for the sub-spacer is formed by forming the pattern of the colored layer 2 (G), then applying the colored layer 2 (B), and coloring layer 2 (G) on the end surface of the colored layer 2 (G). It is formed by patterning the colored layer 2 (B) so that the end face of (B) remains on the surface. The main spacer colored layer laminate 2c-2 is formed with a pattern of the colored layer 2 (R), and then the colored layer 2 (B) is applied, and the base layer of the main spacer that rides on the colored layer 2 (R). The colored layer 2 (B) is formed by patterning so that the colored layer 2 (B) in the region to be stacked. Therefore, the height of the colored layer laminated portion 2c-2 for the main spacer is higher than the height of the colored layer convex portion 2b-2 for the sub-spacer.

  FIG. 5B shows a state in which a resist 3 for forming BM and spacers is applied on the configuration of FIG. Here, as described above, the presence of the BM space 2a, the sub-spacer colored layer projection 2b-2, and the main spacer colored layer laminate 2c-2 causes a difference in height on the surface of the resist 3 as well. ing. That is, 3c-2 on the colored layer laminate portion 2c-2 for the main spacer is the highest, next 3b-2 on the colored layer convex portion 2b-2 for the sub-spacer, and 3a on the BM space portion 2a. It becomes in order.

  FIG. 5C shows a state in which the pattern of BM (4a), the sub-spacer resist pattern 4b-2, and the main spacer resist pattern 4c-2 are formed by performing exposure and development in the form of FIG. 5B. Show. Here, the photomask used for exposure has the above-described height difference on the surface of the resist 3, and thus may be a photomask having a constant transmittance. However, the BM (4a) pattern and sub-spacer can be more reliably used. In order to match the height of the resist pattern 4b-2 for main and the resist pattern 4c-2 for main spacer to the target, it is preferable to use a gradation mask having light transmitting portions having different transmittances. In either case, the BM and the spacer can be created in the same process.

  FIG. 5D shows a form in which the overcoat layer 5 is laminated on the form shown in FIG. By using a transparent resin for the overcoat layer, the insulating property of the spacer portion can be preferably increased. As described above, the entire main spacer 6c-2 and sub-spacer 6b-2 are formed, and the second embodiment (FIG. 3) of the color filter substrate of the present invention is manufactured.

  The thickness of the BM is 1.0 to 3.5 μm, and the width of the central portion of the thickness in the sectional view is 3.0 to 40 μm. The film thickness of the red, blue and green colored layers is 1.5 to 3.5 μm.

  The liquid crystal display device of the present invention has a known configuration except that the color filter substrate includes the color filter substrate of the present invention, and can be manufactured by a method similar to the conventional manufacturing method.

  Hereinafter, materials constituting the color filter substrate of the present invention will be described.

  The BM (in the present invention, a part of the BM also serves as a spacer, but since the same material is used, it will be described as a BM material hereinafter) is formed in a matrix by a photolithography method using a black photosensitive resin. As the black color material, carbon black, titanium oxide, or the like can be used.

  For example, the black photosensitive resin and the colored photosensitive resin used for forming the BM and the colored layer are obtained by dispersing a pigment in a resin binder using a dispersant, and adding a monomer, an initiator, a sensitizer, a solvent, and the like to the dispersion. It is prepared by adding.

  In the color filter substrate of the present invention, the black photosensitive resin and the colored photosensitive resin used for forming the BM and the colored layer are mainly composed of a resin binder and an initiator, and the resin binder is photopolymerized, thermally polymerized, or photopolymerized. It undergoes three-dimensional crosslinking through polymerization and thermal polymerization. By three-dimensionally cross-linking the BM and the resin binder of the colored layer, it is possible to suppress the thickness of the BM and the colored layer from being reduced by the load in the panel assembling process.

  Examples of resin binders suitable for photopolymerization include acrylate resins, examples of resin binders suitable for thermal polymerization include epoxy resins, and examples of resin binders suitable for photopolymerization and thermal polymerization include epoxy acrylate resins. It is done.

  Examples of the alkali-soluble resin include (meth) acrylic resins containing maleic acid, maleic resins, rosin resins, and novolac resins.

  As the polymerizable monomer, the following monomers can be mixed or used alone. For example, monomers containing a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate , (Meth) acrylic acid esters such as dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, or pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl Examples include (meth) acrylates, hexa (meth) acrylates of caprolactone adducts of dipentaerystol hexa (meth) acrylate, and melamine (meth) acrylates.

It is preferable that a part of the polymerizable monomer is a polymerizable monomer containing a carboxyl group-containing polyfunctional monomer. For example, pentaerythritol or a derivative thereof may be used. These monomers can increase the mixing ratio of the polymerizable monomer while maintaining the photolithographic suitability such as developability without increasing the other resin solid content and further maintaining the elastic recovery rate of the spacer.

  Examples of the photopolymerization initiator include acetophenones such as acetophenone, 2,2′-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, thioxanthone, 2- Sulfur compounds such as chlorothiosanson, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethyl Anthraquinones such as anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- Triazines such as (4′-methoxynaphthyl) -6-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine, Α-amino ketone photopolymerization such as organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. Agent 2-methyl-1 [4 -(Methylthio) phenylto2] -morpholinopropan-1-one (Irgacure 907: manufactured by Ciba Specialty Chemicals: trade name), 2-benzyl-2-dimethylaminoate (4-morpholinophenyltobunon- 1 (Irgacure 369: manufactured by BASF).

  For the red colored layer, for example, C.I. I. Pigment Red 7, 14, 41, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 179, 184, 185, Red pigments such as 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 can be used, and a yellow pigment and an orange pigment can also be used in combination.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 181,182,187,188,193,194,199,198,213,214, and the like.

  Examples of the orange pigment include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like.

  Examples of the green colored layer include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, and 58 can be used, and a yellow pigment can be used in combination. As the yellow pigment, the same pigments as those mentioned for the pigment used in the red colored layer can be used.

  For the blue colored layer, for example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like can be used, and a purple pigment can be used in combination. Examples of purple pigments include C.I. I. PigmentViolet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like.

  When the blue colored layer contains at least one of a metal phthalocyanine blue pigment and a dioxazine purple pigment among these pigments, it is easy to obtain a phase difference close to zero. The amount used is 40 to 100% by weight of the metal phthalocyanine blue pigment and 1 to 50% by weight of the dioxazine violet pigment based on the total weight of the pigment. From the above point, it is preferable that the metal phthalocyanine blue pigment is 50 to 98% by weight, and the dioxazine purple pigment is 2 to 25% by weight.

In the above, examples of the metal phthalocyanine blue pigment include C.I. I. PigmentBlue
15: 6, and dioxazine-based purple pigments include C.I. I. PigmentViolet 23 is preferable in terms of excellent light resistance, heat resistance, transparency, coloring power, and the like.

  The red colored layer, green colored layer, and blue colored layer may be used in combination with an arbitrary dye in addition to the pigment.

  Hereinafter, the color filter substrate of the present invention will be described in more detail with reference to examples. Conditions common to the examples 1 to 3 will be described first.

[Pigment selection]
The following were used as pigments for forming the colored layer.
<Red Pigment 1 (R-1)>
Red pigment 1 (CI Pigment Red 254, “IR Gap HOR RED B-CF” manufactured by BASF; R-1) was used.
<Red Pigment 2 (R-2)>
Red pigment 2 (CI Pigment Red 177, “CROMOPHTAL RED A2B” manufactured by BASF; R-2) was used.

<Green Pigment 1 (G-1)>
Green pigment (CI Pigment Green 36, “LIONOL GREEN 6YK” manufactured by Toyo Ink Co., Ltd .; G-1) 500 parts, sodium chloride 1300 parts, and diethylene glycol (Tokyo Kasei Co., Ltd.) 270 parts made of stainless steel 1 gallon kneader (Made by Inoue Seisakusho) and kneaded at 70 ° C. for 3 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It was dried at 80 ° C. for 24 hours to obtain 496 parts of a salt milled pigment.

<Yellow Pigment 1 (Y-1)>
200 parts of yellow pigment (CI Pigment Yellow 138, “PALIOTOL YELLOW K0961HD” manufactured by BASF), 1500 parts of sodium chloride, and 270 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 gallon kneader (manufactured by Inoue Seisakusho) The mixture was kneaded at 60 ° C. for 6 hours. Next, this mixture is poured into about 5 liters of warm water, stirred in a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol. And dried at 80 ° C. for 24 hours to obtain 196 parts of a salt milled pigment.

<Blue Pigment 1 (B-1)>
Blue Pigment 1 (CI Pigment Blue 15: 6, “LIONOL BLUE ES” manufactured by Toyo Ink Co., Ltd.) was used.

<Purple Pigment 1 (V-1)>
Purple Pigment 1 (CI Pigment Violet 23, “LIONOGEN VIOLET RL” manufactured by Toyo Ink Co., Ltd.) was used.

[Preparation of acrylic resin solution]
The preparation of the acrylic resin solution will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction. .
Methacrylic acid 20.0 parts Methyl methacrylate 10.0 parts n-Butyl methacrylate 35.0 parts 2-Hydroxyethyl methacrylate 15.0 parts 2,2'-azobisisobutyronitrile 4.0 parts paracumylphenol ethylene oxide modification Acrylate 20.0 parts ("Aronix M110" manufactured by Toa Gosei Co., Ltd.)

  After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour, An acrylic resin solution was obtained. The weight average molecular weight of this acrylic resin was about 40,000.

  After cooling to room temperature, about 2 g of the resin solution was sampled and heat-dried at 180 ° C. for 20 minutes, the non-volatile content was measured, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20 wt%. An acrylic resin solution was prepared.

[Preparation of pigment dispersion]
The mixture of the composition (% by weight) shown in Table 1 below was uniformly stirred and mixed, then dispersed with an Eiger mill for 2 hours using zirconia beads having a diameter of 0.5 mm, filtered through a 5 μm filter, and pigment dispersion RP -1, GP-1, and BP-1.

[Preparation of colored composition]
After stirring and mixing the mixture of the composition (% by weight) shown in Table 2 to be uniform, the mixture is filtered through a 1 μm filter, and RR-1 (red) and GR-1 (green) which are colored compositions of each color. ), BR-1 (blue).

Specific examples of the materials shown in Table 2 are shown below.
Monomer: Trimethylolpropane triacrylate (Shin Nakamura Chemical "NK Ester ATMPT")
Photoinitiator: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907” manufactured by BASF)
Sensitizer: 4,4′-bis (diethylamino) benzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)
Organic solvent: cyclohexanone

<Example 1>
Using the colored composition of Table 1, red, green, and blue colored layers were formed on a glass substrate.

That is, RR-1 which is a red coloring composition was apply | coated to the transparent substrate by die coating so that it might become a finished film thickness of 2.5 micrometers. After drying under reduced pressure, light from a high-pressure mercury lamp was irradiated at 50 mJ / cm ² through a photomask having a stripe pattern for pixel formation, and developed with an alkali developer for 60 seconds. Then, it hardened | cured for 30 minutes at 230 degreeC, and formed the red colored layer. The finished film thickness means the film thickness after hardening at 230 ° C. for 30 minutes.

  Next, in the same manner, GR-1 which is a green coloring composition is applied by die coating so that the finished film thickness becomes 2.5 μm, dried under reduced pressure, exposed and developed through a photomask, and at 230 ° C. By hardening for 30 minutes, a green colored layer was formed.

  Similarly, BR-1 which is a blue coloring composition is applied by die coating so that the final film thickness is 2.5 μm, dried under reduced pressure, exposed and developed through a photomask, and 30 ° C. at 30 ° C. The blue colored layer was formed by carrying out partial hardening.

  In the exposure for forming the red, green, and blue colored layers, the adjacent colored layers do not overlap each other at the position where the BM that functions only as the BM is disposed, and is 3.0 to 4.0 μm in a sectional view. A space portion having a width (2a in FIG. 4A) is formed, and adjacent colored layers do not overlap each other at the position where the sub-spacer is formed, and the upper base of the inverted trapezoidal shape is 2.5 μm in a sectional view. A space portion (2b-1 in FIG. 4 (a)) having a width of 5 mm is formed, and the colored spacer pattern formed in the subsequent process is formed on the end surface of the colored layer pattern formed in the previous process at the position where the main spacer is formed. Each photomask was designed so that the end surface climbed and a convex portion (2c-1 in FIG. 4A) was formed.

Thereafter, BM and a spacer forming resist are applied by die coating so that the height of the main spacer portion is 2.5 μm, and then the light of the high-pressure mercury lamp is passed through a photomask having a light transmission portion for BM and a light transmission portion for spacer. The film was irradiated with 50 mJ / cm ² and developed with an alkali developer for 60 seconds. Then, it hardened | cured for 30 minutes at 230 degreeC, and formed BM, the subspacer, and the main spacer collectively.

In addition, the alkali developing solution in the above-mentioned each colored layer, BM, and spacer formation was set as the following compositions.
Sodium carbonate 1.5% by weight
Sodium bicarbonate 0.5% by weight
90.0% by weight of water

  An overcoat layer was formed as a protective film on the entire surface of the substrate obtained as described above. A thermosetting transparent resin was used for the overcoat layer, which was applied by a die coating method and dried under reduced pressure, followed by baking at 230 ° C. for 30 minutes.

  As described above, the color filter substrate of the first embodiment of the present invention shown in FIG. 1 was obtained. The difference in height between the main spacer and the sub-spacer of the color filter substrate was 0.4 μm, which was confirmed to be within the scope of the present invention.

<Example 2>
In the production of the color filter substrate of Example 2, in the exposure for forming the red, green, and blue colored layers, the adjacent colored layers do not overlap with each other at the position where the sub-spacer is formed. A manufacturing method similar to that of Example 1 was used except that each photomask designed to form a space portion having a width of 0.0 μm was used.

  As a result, the color filter substrate of the modification of the first embodiment of the present invention shown in FIG. 2 was obtained. The difference in height between the main spacer and the sub-spacer of the color filter substrate was 0.5 μm, which was confirmed to be within the scope of the present invention.

<Example 3>
In the production of the color filter substrate of Example 3, in the exposure for forming the red, green, and blue colored layers, the color formed on the end face of the colored layer pattern formed in the previous step at the position where the sub-spacer is formed in the subsequent step. The end surface of the layer pattern rides up to form a convex portion (2b-2 in FIG. 5A), and the main spacer is formed at a region that becomes the base of the main spacer of the colored layer pattern formed in the previous step. A manufacturing method similar to that in Example 1 except that each of the photomasks designed so that the colored layer patterns to be formed in the subsequent process overlap and a stacked portion (2c-2 in FIG. 5A) is formed is used. It was.

  As a result, the color filter substrate of the second embodiment of the present invention shown in FIG. 3 was obtained. The difference in height between the main spacer and the sub-spacer of the color filter substrate was 0.6 μm, which was confirmed to be within the scope of the present invention.

1, 11... Transparent substrate 2 (R), 12 (R) ... Colored layer (red)
2 (B), 12 (B) ... colored layer (blue)
2 (G), 12 (G) ... colored layer (green)
2a: Space (for black matrix)
2b-1 Space part (for sub-spacer)
2b-2 ... Colored layer protrusion (for sub-spacer)
2c-1 Colored layer convex part (for main spacer)
2c-2 ... Colored layer laminate (for main spacer)
3 .... Resist 3a ... Resist recess (for black matrix)
3b-1 ... Resist recess (for sub-spacer)
3c-1 ... Resist recess (for main spacer)
3b-2 ... Resist convex part (for sub-spacer)
3c-2 ... Resist recess (for main spacer)
4a, 14a-1, 14a-2 Black matrix 4b-1, 4b-2 ... Resist pattern (for sub-spacer)
4c-1, 4c-2 ... Resist pattern (for main spacer)
5, 15... Overcoat layers 6b-1, 6b-2, 16b ... Sub-spacers 6c-1, 6c-2, 16c ... Main spacers

Claims (7)

In a color filter substrate that is used in a liquid crystal display device and includes a colored layer, a black matrix, and a spacer that holds a cell gap between the TFT array substrate,
A color filter substrate, wherein a part of the black matrix forms a convex portion of the spacer.   2. The color filter substrate according to claim 1, wherein the spacer is at least two kinds of spacers having different heights.   3. The lower part of at least the lowest spacer among the two or more kinds of spacers having different heights is present at a boundary portion of different colored layers with a width of 1 to 5 μm in cross-sectional view. Color filter substrate.   Among the two or more types of spacers having different heights, there is a boundary portion of different colored layers below at least the highest spacer, and one colored layer forms a convex portion at the boundary portion. The color filter substrate according to claim 2, wherein   3. The color filter substrate according to claim 2, wherein among the two or more types of spacers having different heights, different colored layers are laminated under at least the highest spacer. 4.   The difference in height between the highest spacer and the lowest spacer among the two or more types of spacers having different heights is 0.3 to 0.7 µm. The color filter substrate according to item.   A liquid crystal display device comprising the color filter substrate according to claim 1.

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