JP5970877B2 - Color filter substrate manufacturing method and display device manufacturing method - Google Patents

Description

  The present invention relates to a method for manufacturing a color filter substrate and a method for manufacturing a display device, and more particularly to a method for manufacturing a color filter substrate and a method for manufacturing a display device that can improve the luminance of a blue colored layer.

  In recent years, with the development of personal computers, flat-screen televisions, etc., the demand for color liquid crystal display devices tends to increase. This color liquid crystal display device generally includes a group of three primary color layers having a blue color layer (R), a green color layer (G), and a blue color layer (B), and a light shielding portion (black matrix) for partitioning them. The color filter is provided, and the electrodes corresponding to the respective pixels of the blue colored layer (R), the green colored layer (G), and the blue colored layer (B) of the color filter are turned on and off. The liquid crystal operates as a shutter, and light passes through each pixel of each of the colored layers (R), (G), and (B), and color display is performed.

  By the way, there are two types of color filters: a type using a dye as a coloring material constituting the colored layer and a type using a pigment. Since the dye is dissolved in the binder at the molecular level, it has the advantage that the transmittance of the colored layer can be increased compared to the color filter using the pigment, and the brightness can be improved. The dye is disadvantageous in that it is more likely to deteriorate than a pigment in terms of light resistance and heat resistance and is less reliable.

  In general, a pigment is a substance in which a large number of dye molecules aggregate and lose solubility, and the pigment itself is not originally light-transmitting, but in order to impart light-transmitting properties, pigment particles are made 100 nm in the presence of a dispersant. A certain degree of light transmittance can be ensured by using the finely divided front and rear. For this reason, at present, it can be said that a pigment dispersion type color filter having excellent heat resistance and light resistance is common. Pigment-dispersed color filters using these pigments have been widely used for colorization of liquid crystal displays, and so far a great number of colors have been developed, and a certain degree of freedom in selection can be secured. It is thought that.

  However, recently, in response to the demand for higher brightness of the screen in the color filter display device, for the pixels of the blue colored layer (R), even if a pigment having the highest transmittance among currently available pigment systems is applied, It cannot be said that sufficient light transmittance can be ensured. For this reason, a proposal has been made to use a triphenylmethane dye having excellent light transmittance and a certain degree of heat resistance (Patent Document 1).

JP 2010-243960 A

  However, even triphenylmethane dyes are inferior to pigments in terms of heat resistance and light resistance. For example, a blue colored layer coating solution containing triphenylmethane dyes is provided on the substrate. In the case of baking at a baking temperature around 230 ° C. after exposure and development, the dye itself contained in the blue colored layer is attacked by active oxygen (oxygen radical) generated at a high temperature and discolored. In comparison, the chromaticity is changed and the light transmittance is extremely deteriorated.

  Also, in a method for manufacturing a display device, the method includes a cell combination step in which a color filter substrate and a display array substrate are integrated with a predetermined gap provided through a spacer, and liquid crystal is injected into the predetermined gap. In general, before this cell combining step, a polyimide film is previously applied so as to cover the colored layer of the color filter substrate, and an alignment film forming step for performing a rubbing treatment after drying and firing is generally provided. Also in the process, there is a baking process for baking a polyimide film as a liquid crystal alignment film. When baking is performed in the baking step of the polyimide film, when the baking is performed at a low temperature, the blue colored layer containing the triphenylmethane dye does not fade, but the polyimide film cannot be sufficiently crosslinked. On the other hand, when baking at a high temperature, the polyimide film is sufficiently cross-linked and does not cause a problem as a film characteristic, but the blue colored layer containing the triphenylmethane dye is faded, which may cause a problem as a display device.

  The present invention was devised under such circumstances, and its purpose is to manufacture a color filter substrate capable of realizing high brightness in order to meet the demand for high brightness of the screen in the color filter display device. A method and a manufacturing method of a display device are provided.

In order to solve such a problem, the present invention is a method for producing a color filter substrate having a blue colored layer on a substrate, and the method comprises forming a colored layer on a substrate. The colored layer forming step includes providing a colored layer base layer containing a coloring material containing a dye, and includes exposure, development, and baking, and the baking is at most a pressure of 6.2 × 10 ⁻⁶ Torr. It is configured to be performed in the atmosphere.

  In a preferred embodiment of the method for producing a color filter substrate in the present invention, the dye is configured as a blue dye.

  In a preferred embodiment of the method for producing a color filter substrate in the present invention, the blue dye is configured to contain at least a triphenylmethane dye.

  As a preferred embodiment of the method for producing a color filter substrate in the present invention, the firing temperature in the firing is configured to be 240 ° C. at the highest.

  As a preferable aspect of the method for producing a color filter substrate in the present invention, the firing temperature in the firing is configured to be 180 to 240 ° C.

  As a preferred embodiment of the method for producing a color filter substrate in the present invention, the content ratio of the triphenylmethane dye to the total amount in the colorant is 30 wt% or more.

  As a preferred embodiment of the method for producing a color filter substrate in the present invention, the color filter substrate is configured to further contain a pigment-based color material.

In a preferred embodiment of the method of manufacturing a color filter substrate of the present invention, the colored layer base layer, or the coating of the colored layer forming coating solution is formed by laminating a film for wear color layer formation.

A method of manufacturing a display device according to the present invention includes a step of manufacturing and preparing a color filter substrate having a blue colored layer containing a blue colored material containing a triphenylmethane dye on a substrate, a scanning line, and a switching circuit A step of manufacturing and preparing a display array substrate having the above, and integrating the prepared color filter substrate and the display array substrate with a predetermined gap therebetween via a spacer. And a cell combining step for injecting liquid crystal into the display device, wherein before the cell combining step, a polyimide film is applied so as to cover the colored layer of the color filter substrate, and after drying and baking alignment film forming step is provided to perform the alignment process, carried out in an atmosphere firing at most the pressure 6.2 × 10 ^-6 Torr of polyimide film in the orientation film forming step Configured so that.

  As a preferable aspect of the method for producing a display device in the present invention, the firing temperature in the firing is configured to be 180 ° C to 240 ° C.

  As a preferred embodiment of the method for producing a display device in the present invention, the content ratio of the triphenylmethane dye to the total amount in the blue colorant is 30 wt% or more.

The method for producing a color filter substrate of the present invention has a blue colored layer forming step of forming a blue colored layer on a substrate, and the blue colored layer forming step contains a blue colored material containing a triphenylmethane dye. Including a blue colored layer base layer, exposing, developing, and then firing, and the firing operation is performed in an atmosphere at a pressure of at most 6.2 × 10 ⁻⁶ Torr. Therefore, the generation of active oxygen (oxygen radicals) is reduced even at high temperatures, the discoloration of the dye itself is reduced, and a decrease in light transmittance can be prevented. Further, the method for manufacturing a display device according to the present invention is a cell combination in which a color filter substrate and a display array substrate are integrated with a predetermined gap provided via a spacer, and liquid crystal is injected into the predetermined gap. And the operation of baking the polyimide film in the alignment film forming step performed before the cell combining step is performed in an atmosphere of pressure 6.2 × 10 ⁻⁶ Torr at the highest. Further, it is possible to prevent a decrease in light transmittance due to deterioration of the blue colored layer or the polyimide film.

1A to 1E are cross-sectional views for illustrating an example of a method for manufacturing a color filter substrate of the present invention over time. FIG. 2 is a cross-sectional view for explaining an example of a color filter substrate and a display array substrate for constituting a display device. FIG. 3 is a cross-sectional view of a display device formed by combining a color filter substrate and a display array substrate.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited to the form demonstrated below, In the range which does not deviate from a technical thought, it can implement in various deformation | transformation. In the accompanying drawings, the vertical and horizontal scales may be exaggerated for the sake of explanation, and the actual scales may differ.

  First, an example of a method for manufacturing a color filter substrate of the present invention will be described with reference to FIG.

[Color filter substrate manufacturing method]
(Formation of light shielding part)
As shown in FIG. 1A, a light shielding portion 12 (sometimes referred to as a so-called black matrix) is formed on a substrate 10 in a predetermined pattern.

  Examples of the method for forming the light shielding portion 12 include a photolithography method, various pattern printing methods, and various plating methods.

  The light shielding portion 12 is usually configured as a lattice-shaped light shielding layer, and is usually configured using a photoresist, a printing ink, or a metal such as chromium containing a black pigment, a binder resin, and a solvent. Examples of the black pigment include carbon black and titanium black. Examples of the binder resin include a benzyl methacrylate: styrene: acrylic acid: 2-hydroxyethyl methacrylate copolymer. As a solvent, it can select and use from well-known various.

  In addition, the base material 10 will not be specifically limited if it is a transparent substrate with respect to visible light, The thing similar to the transparent substrate used for a general color filter can be used. Specifically, a rigid material such as quartz glass, Pyrex (registered trademark) glass, or synthetic quartz, or a transparent flexible material having flexibility such as a transparent resin film or an optical resin plate can be used.

(Formation of colored layer)
A red colored layer 13R, a green colored layer 13G, and a blue colored layer 13B are sequentially formed so as to cover predetermined pixels defined by the light shielding portion 12 in plan view.

  FIG. 1B shows a state in which the red colored layer 13R is formed. In forming the red colored layer 13R, the following steps can be adopted.

  First, a red colored layer base layer is formed first. That is, a coating solution for forming a red colored layer containing a photosensitive resin, a coloring material, and various additives on the substrate 10 is applied by a general coating method such as a spin coating method, a die coating method, or a printing method. Applying to form a red colored layer base layer, or forming a colored layer forming film (dry film) containing a photosensitive resin, a coloring material, and various additives on the substrate 10 such as a laminate It can be laminated by a general film laminating method to form a red colored layer base layer. Further, if necessary, the applied colored layer forming coating solution (red colored layer base layer) or the laminated colored layer forming film (red colored layer base layer) may be pre-baked (prebaked). Good.

  Next, exposure and development operations, which are patterning steps of the red colored layer base layer, are performed, and then a baking operation is performed.

  As a method of exposing the red colored layer base layer, for example, a method of exposing using a photomask or the like, or a method of irradiating energy in a pattern using a laser or the like can be used. About the energy irradiated, the irradiation method of energy, etc., it can determine suitably according to the kind etc. of photosensitive resin contained in the said coating liquid for red colored layer formation. Further, the developing method performed after exposure is not particularly limited, and a developing method similar to that for forming a general colored layer can be used.

The baking operation performed after development is not particularly limited, and the baking may be performed in a normal atmospheric pressure atmosphere. The firing temperature is, for example, about 200 ° C to 250 ° C.
Examples of the coloring material used for the red colored layer 13R include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments, and isoindoline pigments. These pigments may be used alone or in combination of two or more.

  Next, as shown in FIG. 1C, a green colored layer 13G is formed. In forming the green colored layer 13G, a process according to the process of the red colored layer 13R described above can be adopted. That is, after the green colored layer base layer is formed, exposure and development operations, which are patterning steps of the green colored layer base layer, are performed, followed by firing in a normal atmospheric pressure atmosphere.

  Examples of coloring materials used for the green colored layer 13G include phthalocyanine pigments such as halogen polysubstituted phthalocyanine pigments or halogen polysubstituted copper phthalocyanine pigments, triphenylmethane basic dyes, isoindoline pigments, and isoindolinone. And pigments. These pigments or dyes may be used alone or in combination of two or more.

  Note that the order of forming the green colored layer 13G and the step of forming the red colored layer 13R can be reversed.

Next, as shown in FIG. 1D, a blue colored layer 13B is formed.
First, a blue colored layer base layer is formed first. That is, on the base material 10, a blue coloring material composed of a triphenylmethane dye represented by the following structural formula (1), other blue coloring materials contained as necessary, a photosensitive resin, various additives, and the like The blue colored layer forming coating solution containing, is applied by a general coating method such as a spin coating method, a die coating method, or a printing method to form a blue colored layer base layer, or on a base material, A colored layer forming film containing a blue coloring material comprising a triphenylmethane dye represented by the following structural formula (1), another blue coloring material contained as necessary, a photosensitive resin, and various additives (Dry film) can be laminated by a general film laminating method such as laminating to form a blue colored layer base layer. Further, if necessary, the applied colored layer forming coating solution (blue colored layer base layer) or the laminated colored layer forming film (blue colored layer base layer) may be pre-baked (prebaked) or the like. Good.

In the structural formula (1), R1 as a substituent is an alkyl group having 1 to 10 carbon atoms such as —H, —CH ₃ , or C ₂ H ₅ , a haloalkyl group such as a trifluoromethyl group, a phenyl group or naphthyl. An aryl group such as a group, an alkoxyl group such as a methoxy group and an ethoxy group, a halogen atom such as fluorine and iodine, and a cyano group, and the substituents R2 and R3 are independently of each other -H, C 1-10 alkyl groups such as —CH ₃ , C ₂ H ₅ , haloalkyl groups such as trifluoromethyl group, aryl groups such as phenyl group and naphthyl group, alkoxyl groups such as methoxy group and ethoxy group, fluorine - can be selected from halogen atom and a cyano group iodine are substituents R4 and R5, independently of one _{another, -H, -CH 3, C 2} H 5, carbon atoms, such as 1 It can be selected from 0 alkyl groups, haloalkyl groups such as trifluoromethyl groups, aryl groups such as phenyl groups and naphthyl groups, alkoxyl groups such as methoxy groups and ethoxy groups, halogen atoms such as fluorine and iodine, and cyano groups. .

  In addition to the blue coloring material composed of such a triphenylmethane dye, another blue coloring material can be further contained. Examples of other blue coloring materials include copper phthalocyanine pigments, anthraquinone pigments, indanthrene pigments, indophenol pigments, cyanine pigments, dioxazine pigments, and the like. These pigments may be used alone or in combination of two or more. Furthermore, a dye-based coloring material having excellent heat resistance can also be added.

  The content ratio of the blue coloring material containing such a triphenylmethane dye is 30% or more, particularly 30% to 70%, more preferably 70% to 100% with respect to the total amount in the blue coloring material to be used. It is preferable to do. Such a content rate represents the ratio of the weight of the triphenylmethane dye to the total weight of the blue coloring material in%.

  If this value is less than 30%, the light transmittance of the blue colored layer based on the use of the dye cannot be improved, and there is a disadvantage that it cannot contribute to the improvement of the luminance of the display panel.

  In addition, the content rate of the whole blue coloring material with respect to the whole weight (solid content) of a blue coloring layer shall be 9.5%-23%.

  Next, exposure and development operations, which are patterning steps of the blue colored layer base layer, are performed, and then a baking operation is performed. About operation of exposure and image development, it can carry out according to the red colored layer etc. which were mentioned above, for example.

The main part of the present invention is that the baking operation performed after development is performed in an atmosphere at a pressure of 6.2 × 10 ⁻⁶ Torr at the highest. The pressure here is the pressure in the chamber or the atmospheric pressure.

Preferred pressure, it is preferable in the range of ^{3.2 × 10 -6 Torr~6.2 × 10 -6} Torr. When the pressure is higher than 6.2 × 10 ⁻⁶ Torr, active oxygen (oxygen radical) may be generated at a desired baking temperature, and the dye itself may be faded, resulting in a decrease in light transmittance of the blue colored layer. There is a risk that. Moreover, when it is made lower than 3.2 × 10 ⁻⁶ Torr, it takes time for evacuation, and thus production efficiency may be lowered.

  The firing temperature in the firing operation is at most 240 ° C., particularly 180 ° C. to 240 ° C., more preferably 190 ° C. to 230 ° C. Although the lower limit of the firing temperature varies depending on the components of the colored layer and the like, it is not certain. However, if this value becomes as low as about 170 ° C., for example, the gas generated in the colored layer is sufficiently diffused. There is a risk that it cannot be done. Further, firing at a temperature higher than 240 ° C. is not preferable because it may damage the colored layer. Further, when the firing temperature is lower than 180 ° C., the film may not be completely cured and the product quality may be impaired.

  Such a blue colored layer may be fired using, for example, a heating device installed in a vacuum chamber.

  Such a blue colored layer is preferably formed last in the formation of the colored layer in order to avoid as much as possible thermal damage caused by firing performed each time the colored layer is formed. That is, in this embodiment, it is desirable to form a blue colored layer last after forming a red colored layer and a green colored layer.

  In this manner, the color filter substrate of the present invention including the red colored layer 13R, the green colored layer 13G, and the blue colored layer 13B is manufactured as shown in FIG. The colored layer 13 is patterned in a state in which the red colored layer 13R, the green colored layer 13G, and the blue colored layer 13B are sequentially arranged, but the pattern arrangement is not particularly limited to the illustrated one. A known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used, and the area of each colored layer can be arbitrarily set.

In the present invention, it can be contained at a high content of 30% or more with respect to the total amount in the blue colorant using the triphenylmethane dye. This is because it is performed in an atmosphere of 6.2 × 10 ⁻⁶ Torr.

  Next, as shown in FIG. 1F, the transparent electrode layer 18 is formed on the colored layer 13 having the red colored layer 13R, the green colored layer 13G, and the blue colored layer 13B. Examples of the material for forming the transparent electrode layer 18 include a metal oxide having transparency and conductivity. Examples of such a metal oxide include indium tin oxide (ITO), indium oxide, zinc oxide, and stannic oxide. The film thickness of the transparent electrode layer 18 is 50 nm to 1500 nm, and more preferably 120 nm to 1200 nm.

  As a method for forming the transparent electrode layer 18, for example, a vapor deposition method or a sputtering method may be used. An overcoat layer (protective film) or the like may be formed before forming the transparent electrode layer 18.

[Description of display array substrate]
Next, the display array substrate (liquid crystal display substrate) will be described with reference to FIG.

  The display array substrate 100 shown on the lower side of FIG. 2 is disposed so as to face the color filter substrate 30 described above, and can be integrated to form a display device. In FIG. 2, the color filter substrate 30 disposed to face is also described, and the color filter substrate 30 shown in FIG. 2 is formed on the alignment film on the transparent electrode layer 18 in order to form a display device. The state in which 20 is formed is depicted. The alignment film 20 is usually provided at the time of the next cell combination step for completing the manufacturing process of the color filter substrate 30 and forming a display device. The cell combination process and the alignment film 20 will be described in detail later.

  As shown in FIG. 2, the display array substrate 100 is configured by a scanning line (not shown), an interlayer insulating film 60, and a large number of pixel electrodes 65a arranged in a matrix on a light-transmitting substrate 55. A structure having a transparent electrode 65, a signal line 70, a protective film (passivation film) 75, a switching circuit portion (not shown), and an alignment film 80 is provided.

  Although the scanning lines are not displayed in the drawing, for example, the scanning lines are arranged so as to correspond to one row (a horizontal direction in the drawing) of a large number of pixel electrodes 65a arranged in a matrix. It is comprised so that it may extend in the longitudinal direction. Each scanning line can be formed of a metal such as tantalum (Ta) or titanium (Ti), for example. These scanning lines are covered with an interlayer insulating film 60.

  The interlayer insulating film 60 is formed of an electrically insulating material such as silicon oxide, for example, and electrically separates the scanning line and the signal line 70 and electrically connects the pixel electrode 65a and the scanning line. It is formed to separate.

  Each pixel electrode 65a is formed so as to correspond to one pixel in the display device. Examples of the material for forming the pixel electrode 65a include a metal oxide having transparency and conductivity. Examples of such a metal oxide include indium tin oxide (ITO), indium oxide, zinc oxide, and stannic oxide. The film thickness of the formed electrode layer is 50 nm to 1500 nm, more preferably 120 nm to 1200 nm. As a method for forming the pixel electrode 65a, for example, an evaporation method or a sputtering method may be used. The shape of each pixel electrode 65a in plan view can be, for example, a quadrilateral or a polygon such as a hexagon formed by cutting one corner of the quadrilateral into a rectangle, but is not necessarily limited to these shapes. It is not something.

For example, the signal lines 70 are arranged so as to correspond to one column (in the direction of the back side of the paper surface) of a large number of pixel electrodes 65a arranged in a matrix and extend in the longitudinal direction of the column. Configured as follows. Each signal line 70 can be formed of a metal such as tantalum (Ta) or titanium (Ti). These signal lines 70 are covered with a protective film 75.
The protective film 75 is made of, for example, silicon nitride, and functions as a protective film of the main body and acts to electrically separate the signal line 70 and the pixel electrode 65a.

  Although the switching circuit portion is not shown in FIG. 2, the switching circuit portion is arranged corresponding to one pixel electrode 65a one by one, and the pixel electrode 65a corresponding to the switching circuit portion, the scanning line, and the signal line 70 is electrically connected.

  Each switching circuit unit receives a signal from a corresponding scanning line and controls conduction between the signal line 70 and the pixel electrode 65a. Each switching circuit unit can be configured using, for example, one active element. As the active element, for example, a three-terminal element such as a thin film transistor or a two-terminal element such as an MIM (Metal Insulator Metal) diode is used, but is not necessarily limited thereto.

  The alignment film 80 can be configured as a horizontal alignment film that can horizontally align the liquid crystal in the display device, or a vertical alignment film that can vertically align the liquid crystal. Which of the horizontal alignment film and the vertical alignment film is used can be appropriately selected according to the operation mode of the display device. The alignment film 80 formed on the display array substrate 100 side can have the same configuration as the alignment film 20 formed on the color filter substrate 30 side described later.

  Note that the configuration of the display array substrate 100 described above is merely an example, and can be appropriately changed according to the operation method, driving method, application, grade, and the like of the liquid crystal display, and is limited to the above-described embodiment. Without limitation, various modifications are possible.

[Method of manufacturing display device]
A method for manufacturing a display device according to the present invention will be described.

  The display device manufacturing method according to the present invention includes a color filter substrate 30 having a blue coloring layer 13B containing a red coloring layer 13R, a green coloring layer 13G, and a blue coloring material containing a triphenylmethane dye on a base material 10. A step of manufacturing and preparing, a step of manufacturing and preparing the display array substrate 100 having a switching circuit, and the prepared color filter substrate 30 and the display array substrate 100 with a predetermined gap through a spacer. And a cell combination step of injecting liquid crystal into the predetermined gap.

  Then, before the cell combination process, a polyimide film is applied so as to cover the colored layers (13R, 13G, 13B) of the color filter substrate 30, and alignment film formation such as rubbing is performed after drying and baking. Steps are provided, and the alignment film 20 is formed so as to cover the colored layers (13R, 13G, 13B) of the color filter substrate 30 as shown in FIG.

The rubbing process is one of alignment film processing methods, and is an operation of adding alignment performance by rubbing the formed polyimide film with a rubbing cloth. In the display device manufacturing method of the present invention, it is particularly important that the baking is carried out in an atmosphere at a pressure of 6.2 × 10 ⁻⁶ Torr even when the polyimide film is formed in the alignment film forming step. It is to be.
Preferred pressure, it is preferable in the range of ^{3.2 × 10 -6 Torr~6.2 × 10 -6} Torr. When the pressure is higher than 6.2 × 10 ⁻⁶ Torr, when the polyimide film is baked at a desired baking temperature, the generated oxygen radical causes the dye of the blue colored layer to fade, and the blue colored layer transmits light. There is a risk that the rate will decrease. Moreover, when it is made lower than 3.2 × 10 ⁻⁶ Torr, it takes time for evacuation, and thus production efficiency may be lowered.

  The firing temperature in the firing operation is at most 240 ° C., particularly 180 ° C. to 240 ° C., more preferably 190 ° C. to 230 ° C. Further, when the firing temperature is lower than 180 ° C., the film may not be completely cured and the product quality may be impaired.

  Further, the alignment layer 80 on the display array substrate 100 side can be formed by the same method as the alignment layer 20 on the color filter substrate side.

  In this way, the color filter substrate 30 having the alignment layer 20 and the display array substrate 100 having the alignment layer 80 are arranged so that the alignment layer 20 and the alignment layer 80 face each other, as shown in FIG. In a state where the liquid crystal material is disposed, a sealing material (for example, a thermosetting resin) 90 is attached, leaving a filling port filled with the liquid crystal material.

  The gap (cell gap) between the display array substrate 100 and the color filter substrate 30 is kept constant by a spacer (for example, a spherical spacer or a columnar spacer) not shown, and the gap between the two is provided from the filling port. A liquid crystal layer 91 is formed by filling the liquid crystal material. The filling port is sealed.

  As shown in FIG. 3, a backlight unit 95, which is a light source, is disposed behind the light transmissive substrate 55 of the display array substrate 100 to form the display device 1.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not construed as being limited to the following examples.

<< Experimental Example I >>
[Example I-1]
A glass substrate (Corning Corp., 1737 material) was prepared as a base material, and a blue colored layer 13B was formed on the glass substrate after being subjected to a cleaning treatment in the following manner.

That is, after preparing a resin composition for a color filter for a blue pixel as shown below, the photoresist is applied on a substrate by a spin coat method (formation of a blue colored layer base layer), and 80 ° C. · 5 Pre-baking (pre-baking) was performed under the condition of minutes, and ultraviolet exposure (40 mJ / cm ² ) was performed using a predetermined photomask for colored pattern.

Next, after performing spray development using a 0.1% KOH aqueous solution for 60 seconds, a base material having a blue colored layer of a predetermined pattern after development is placed in a vacuum chamber, the pressure in the chamber is lowered, At a high pressure of 6.2 × 10 ⁻⁶ Torr, baking was carried out at 220 ° C. for 60 minutes (post-baking) to form a blue colored layer 13G having a predetermined size pattern for experiments.

<Preparation of resin composition for blue pixel color filter>
The resin composition for a color filter for blue pixels was prepared by taking the following steps.
First, the synthesis resin solution was synthesized in the following manner.

(Synthesis of polymerization resin solution)
A polymerization tank was charged with 63 parts by weight of methyl methacrylate, 12 parts by weight of acrylic acid, 6 parts by weight of 2-hydroxyethyl methacrylate and 88 parts by weight of diethylene glycol dimethyl ether, stirred and dissolved, and then 2,2′- 7 parts by mass of azobisisobutyronitrile was added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. 7 parts by mass of glycidyl methacrylate, 0.4 parts by mass of triethylamine and 0.2 parts by mass of hydroquinone were further added to the obtained solution, and the mixture was stirred at 100 ° C. for 5 hours to obtain a copolymer resin solution (solid content 50%). Got.

  Using the copolymer resin solution (solid content 50%) thus obtained, the following materials were mixed and stirred at room temperature to obtain a curable resin composition as a binder.

(Curable resin composition as binder)
The above copolymer resin solution (solid content 50%): 16 parts by mass Dipentaerythritol pentaacrylate (trade name SR399 manufactured by Sartomer): 24 parts by mass Orthocresol novolak type epoxy resin (Product made by Yuka Shell Epoxy Co., Ltd.) Name Epicoat 180S70): 4 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.): 4 parts by mass Part Diethylene glycol dimethyl ether: 52 parts by mass Using the curable resin composition as the binder thus obtained, a resin composition for a color filter for a blue pixel blended in the following manner was obtained.

(Resin composition for color filter for blue pixels)
Triarylmethane-based color material (manufactured by DIC Corporation, no product name): 30 parts by mass Curable resin composition as the above binder: 300 parts by mass Polymer dispersant (trade name DISPERBYK2000 manufactured by Big Chemie Japan Co., Ltd.) : 500 parts by mass 3-methoxybutyl acetate (solvent): 2500 parts by mass

[Comparative Example I-1]
In Example I-1, the firing conditions were changed to firing (post-bake) for 60 minutes at 220 ° C. in an air atmosphere without using a vacuum chamber.

  Other than that was carried out similarly to the said Example I-1, and formed the blue colored layer 13G of the comparative example I-1 which has a pattern of the predetermined magnitude | size for experiment.

[Comparative Example I-2]
In Example I-1, the firing conditions were changed to firing (post-baking) at 220 ° C. for 60 minutes in a nitrogen atmosphere without using a vacuum chamber. The nitrogen atmosphere was formed by constantly substituting nitrogen while continuously removing the gas in the chamber.

  Other than that was carried out similarly to the said Example I-1, and formed the blue colored layer 13G of the comparative example I-2 which has a pattern of the predetermined | prescribed magnitude | size for experiment.

[Reference Sample I-1]
In Example I-1, the blue colored layer 13G was not fired (post-baked).
Other than that was carried out similarly to the said Example I-1, and formed the blue colored layer 13G of the reference | standard sample I-1 which has a pattern of the predetermined magnitude | size for experiment. That is, it is a sample in which the degradation of the triphenylmethane dye by firing is not caused.

  The samples of Examples and Comparative Examples thus formed, and the reference sample that is not baked are subjected to an optical property test in the following manner to determine the chromaticity x, y, luminance Y, and transmittance at a wavelength of 450 nm. At the same time, the color difference (ΔE * ab) after firing of each sample was found with reference to a reference sample that was not fired.

<Optical characteristics test>
The chromaticity x, y and luminance Y of the blue transmitted light transmitted through the blue colored layer 13G in each of the above samples and the transmittance at a wavelength of 450 nm were measured using a microspectroscope OSP-SP2000 (manufactured by OLYMPUS). As the light source, “standard light C” whose relative spectral distribution was determined by CIE was used. Furthermore, the color difference (ΔE * ab) after firing of each sample was determined with reference to a reference sample that was not fired.
The results are shown in Table 1 below.

  From the results shown in Table 1, it can be seen that the sample of Example I-1 in the present invention has the smallest color difference (ΔE * ab) after firing, and the triphenylmethane dye is hardly faded even by firing. . The transmittance is not changed from that before firing.

<< Experimental Example II >>
[Example II-1]
A glass substrate (Corning Corp., 1737 material) was prepared as a base material, and a blue colored layer 13B was formed on the glass substrate after being subjected to a cleaning treatment in the following manner. That is, after preparing a photoresist for forming a blue colored layer as shown below, the photoresist is applied on a base material by a spin coat method (formation of a blue colored layer base layer) at 80 ° C. for 5 minutes. The film was pre-baked (pre-baked) under the above conditions, and was exposed to ultraviolet rays (300 mJ / cm ² ) using a predetermined photomask for colored pattern.

Next, spray development using a 0.1% KOH aqueous solution is performed for 60 seconds, and then a substrate having a blue colored layer of a predetermined pattern after development is placed in a vacuum chamber, the pressure in the chamber is lowered, and the pressure in the chamber is reduced. Was baked (post-baked) at 230 ° C. for 60 minutes in an atmosphere of at most 6.2 × 10 ⁻⁶ Torr to form a blue colored layer 13G having a predetermined pattern for experimentation.

<Preparation of resin composition for blue pixel color filter>
The resin composition for a color filter for blue pixels was prepared by taking the following steps.
First, the synthesis resin solution was synthesized in the following manner.

(Synthesis of polymerization resin solution)
A polymerization tank was charged with 63 parts by weight of methyl methacrylate, 12 parts by weight of acrylic acid, 6 parts by weight of 2-hydroxyethyl methacrylate and 88 parts by weight of diethylene glycol dimethyl ether, stirred and dissolved, and then 2,2′- 7 parts by mass of azobisisobutyronitrile was added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. 7 parts by mass of glycidyl methacrylate, 0.4 parts by mass of triethylamine and 0.2 parts by mass of hydroquinone were further added to the obtained solution, and the mixture was stirred at 100 ° C. for 5 hours to obtain a copolymer resin solution (solid content 50%). Got.

  Using the copolymer resin solution (solid content 50%) thus obtained, the following materials were mixed and stirred at room temperature to obtain a curable resin composition as a binder.

(Curable resin composition as binder)
The above copolymer resin solution (solid content 50%): 16 parts by mass Dipentaerythritol pentaacrylate (trade name SR399 manufactured by Sartomer): 24 parts by mass Orthocresol novolak type epoxy resin (Product made by Yuka Shell Epoxy Co., Ltd.) Name Epicoat 180S70): 4 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.): 4 parts by mass Parts Diethylene glycol dimethyl ether: 52 parts by mass

  Using the curable resin composition as a binder thus obtained, a resin composition for a color filter for a blue pixel blended in the following manner was obtained.

(Resin composition for color filter for blue pixels)
Blue pigment zinc phthalocyanine pigment (product of DIC Co., Ltd., no product name, average primary particle size 50 nm): 70 parts by mass Triarylmethane color material (product of DIC Co., Ltd., no product name): 30 parts by mass The above curable resin composition Product (binder): 300 parts by mass Polymer dispersing agent (trade name DISPERBYK2000 manufactured by BYK Japan KK): 500 parts by mass 3-methoxybutyl acetate (solvent): 2500 parts by mass

[Comparative Example II-1]
In Example II-1 above, the firing was changed to post-baking in the air atmosphere without using a vacuum chamber.

  Other than that was carried out similarly to the said Example II-1, and formed the comparative example II-1 blue colored layer 13G which has a pattern of the predetermined | prescribed magnitude | size for experiment.

[Comparative Example II-2]
In Example II-1, the firing was changed to a post-bake in a nitrogen atmosphere without using a vacuum chamber. The nitrogen atmosphere was formed by constantly substituting nitrogen while continuously removing the gas in the chamber.

  Other than that was carried out similarly to the said Example II-1, and formed the blue colored layer 13G of Comparative Example II-2 which has a pattern of the predetermined magnitude | size for experiment.

[Reference Sample II-1]
In Example II-1, the blue colored layer 13G was not fired (post-baked). Other than that was carried out similarly to the said Example II-1, and formed the blue colored layer 13G of the reference | standard sample II-1 which has a pattern of the predetermined magnitude | size for experiment. That is, it is a sample in which the degradation of the triphenylmethane dye by firing is not caused.

The samples of Examples and Comparative Examples thus formed and the reference sample that is not baked are subjected to optical property tests as described above, and the chromaticity x, y, luminance Y, and transmittance at a wavelength of 450 nm are measured. At the same time, the color difference (ΔE * ab) after firing of each sample was found with reference to a reference sample that was not fired.
The results are shown in Table 2 below.

<< Experimental Example III >>
An alignment film forming step was performed in which a polyimide film was applied on the blue colored layer 13G of the color filter substrate of Example I-1 and subjected to an alignment treatment after drying and baking.

  As firing methods, (1) firing in a pressure atmosphere according to Example I-1 above, (2) firing in an air atmosphere according to Comparative Example I-1, and (3) Comparative Example I above. -2 types of firing in a nitrogen atmosphere according to -2.

  As a result, the transmittance at a wavelength of 450 nm was most excellent in the case of (1).

From the above results, the effects of the present invention are clear. That is, the method for producing a color filter substrate of the present invention includes a blue colored layer forming step of forming a blue colored layer on a substrate, and the blue colored layer forming step includes a blue colored material containing a triphenylmethane dye. Including a blue colored layer base layer containing, exposing, developing, and then firing, the firing operation being performed in an atmosphere at a pressure of at most 6.2 × 10 ⁻⁶ Torr. Therefore, the triphenylmethane dye, which is a blue coloring material, has less fading and the chromaticity does not change, and high brightness can be realized.

Further, in the manufacturing method of the display device of the present invention, since the operation of baking the polyimide film in the alignment film forming step is performed at a pressure of at most 6.2 × 10 ⁻⁶ Torr, It is possible to prevent the luminance of the display device from being lowered during baking, and to achieve high luminance.

  It can be widely used in the electronics industry including flat displays.

DESCRIPTION OF SYMBOLS 10 ... Base material 12 ... Light-shielding part 13 ... Colored layer 13R ... Red colored layer 13G ... Green colored layer 13B ... Blue colored layer 20 ... Alignment film 30 ... Color filter substrate 60 ... Interlayer insulating film 65 ... Transparent electrode 65a ... Pixel electrode 70 ... Signal line 75 ... Protective film (passivation film)
80 ... Alignment film
100 ... array substrate for display

Claims (11)

A method for producing a color filter substrate having a blue colored layer on a substrate,
The manufacturing method is as follows:
Having a colored layer forming step of forming a colored layer on the substrate;
The colored layer forming step includes providing a colored layer base layer containing a coloring material containing a dye, and includes exposure, development, and baking, and the baking is performed in an atmosphere at a pressure of at most 6.2 × 10 ⁻⁶ Torr. A method for manufacturing a color filter substrate.   The method for producing a color filter substrate according to claim 1, wherein the dye is a blue dye.   The method for producing a color filter substrate according to claim 2, wherein the blue dye contains at least a triphenylmethane dye.   The method for manufacturing a color filter substrate according to any one of claims 1 to 3, wherein a baking temperature in the baking is at most 240 ° C.   The method for producing a color filter substrate according to claim 4, wherein a firing temperature in the firing is 180 to 240 ° C. 5.   The method for producing a color filter substrate according to any one of claims 3 to 5, wherein the content ratio of the triphenylmethane dye to the total amount in the colorant is 30 wt% or more.   The method for producing a color filter substrate according to claim 1, further comprising a pigment-based coloring material as the coloring material. The colored layer base layer, production of a color filter substrate according to any one of claims 1 to 7 or the coating of the colored layer forming coating solution is formed by laminating a film for wear color layer formed Method. Producing and preparing a color filter substrate having a blue colored layer containing a blue colored material containing a triphenylmethane dye on a substrate; and
Manufacturing and preparing a display array substrate having scanning lines and switching circuits;
A cell combining step of integrating the prepared color filter substrate and the display array substrate with a predetermined gap through a spacer and injecting liquid crystal into the predetermined gap. A manufacturing method comprising:
Before the cell combination step, a polyimide film is applied so as to cover the colored layer of the color filter substrate, and an alignment film forming step for performing an alignment treatment after drying and baking is provided.
A method for manufacturing a display device, wherein the polyimide film in the alignment film forming step is baked at a pressure of at most 6.2 × 10 ⁻⁶ Torr.   The display device manufacturing method according to claim 9, wherein a baking temperature in the baking is 180 ° C. to 240 ° C.   11. The method for manufacturing a display device according to claim 9, wherein a content ratio of the triphenylmethane dye to the total amount in the blue colorant is 30 wt% or more.

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