JP2002341128A - Method for manufacturing color filter and liquid crystal display element - Google Patents

Method for manufacturing color filter and liquid crystal display element

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Publication number
JP2002341128A
JP2002341128A JP2001144631A JP2001144631A JP2002341128A JP 2002341128 A JP2002341128 A JP 2002341128A JP 2001144631 A JP2001144631 A JP 2001144631A JP 2001144631 A JP2001144631 A JP 2001144631A JP 2002341128 A JP2002341128 A JP 2002341128A
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JP
Japan
Prior art keywords
ink
color filter
resin
layer
color
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2001144631A
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Japanese (ja)
Inventor
Takayoshi Akamatsu
Atsushi Fujiwara
篤 藤原
孝義 赤松
Original Assignee
Toray Ind Inc
東レ株式会社
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Publication date
Application filed by Toray Ind Inc, 東レ株式会社 filed Critical Toray Ind Inc
Priority to JP2001144631A priority Critical patent/JP2002341128A/en
Publication of JP2002341128A publication Critical patent/JP2002341128A/en
Pending legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To reduce difference in quality between a transmissive mode display with a backlight as a light source and a reflective mode display with external light as a light source without increasing the number of times of photolithography by making color purity of a coloring layer in a transmission region higher than that in a reflection region in a color filter for a semitransmissive color liquid crystal display element provided with the transmission region and the reflection region. SOLUTION: The method for manufacturing the color filter forms at least a coloring layer on a substrate with an inkjet device and is characterized by having the color filter provided with the transmission region utilizing light from the backlight and the reflection region utilizing the external light in a pixel and by having the color purity in the transmission region higher than that in the reflection region.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used for a liquid crystal display device which can be used for both transmissive display and reflective display.

[0002]

2. Description of the Related Art Color liquid crystal display devices for mobile applications such as PDAs and mobile phones use a backlight in a dark environment to save power and improve visibility under particularly strong external light such as direct sunlight. Many are used in a transmission mode, and can be displayed in a reflection mode using external light in a bright environment. Such a transflective color liquid crystal display device includes a device provided with a transflective reflective film and a device provided with a transmissive region and a reflective region in one pixel.

[0003]

In a transflective color liquid crystal display device, light is displayed only once through a color filter in a transmissive mode, whereas light is displayed in a reflective mode. Since the image is displayed twice through the color filter, the displayed color is significantly different between the transmission mode and the reflection mode. Also, in the transmission mode, which can be designed by a combination of a backlight and a color filter, the color purity is higher. Most importantly, in the above-mentioned transflective type, while the color purity is reduced in the transmissive mode in which light is sufficiently supplied, when the light intensity is relatively small in a room or the like, the display in the reflective mode is dark, which is desirable. The direction is opposite.

As a method of making the display colors of the transmission region and the reflection region the same, it is conceivable to change the film thickness of the coloring layer and the coloring material of the coloring layer in the transmission region and the reflection region. In either case, two photolithography processes are required for one pixel, which increases the cost.

An object of the present invention is to solve the above-mentioned problems and to provide an inexpensive color filter with a small difference in color between transmissive display and reflective display.

[0006]

The object of the present invention is achieved by the following constitution and manufacturing method. (1) A method for manufacturing a color filter in which at least a colored layer is formed on a substrate by using an inkjet device, wherein the color filter includes a transmission region using backlight light and a reflection region using external light within one pixel. Wherein the transmission region has higher color purity than the reflection region. (2) The method for producing a color filter according to the above (1), wherein more ink droplets adhere to the transmission area than the reflection area. (3) The method for producing a color filter according to the above (1), wherein an ink droplet having a higher density is attached to the transmission area than the reflection area. (4) At least one ink repellent resin layer or ink repellent light-shielding resin black matrix whose surface has a receding contact angle of 20 ° or more with respect to the colored layer forming ink is formed at a predetermined position on the substrate. Next, ink droplets are dropped by using an ink jet device on predetermined portions other than the ink repellent resin layer or the ink repellent light-shielding resin black matrix on the substrate to form a colored layer. 1) The method for producing a color filter according to the above. (5) The color filter according to the above (1), wherein at least one layer of an ink repellent resin layer or an ink repellent light-shielding resin black matrix is formed at a boundary between the transmission area and the reflection area in one pixel. Manufacturing method. (6) The method for producing a color filter according to the above (1), wherein a transparent resin layer is formed on the colored layer. (7) A method for producing a color liquid crystal display device, comprising using the color filter according to (1) to (6).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The substrate used in the color filter of the present invention is a transparent substrate and is not particularly limited. Soda lime glass, borosilicate glass, aluminoborosilicate glass, quartz glass, Inorganic glasses such as soda lime glass coated with silica, and organic plastic films or sheets are preferably used.

In the present invention, at least the colored layer is formed using an ink jet device. A coloring ink, which is a material of a coloring layer, is supplied to the ink jet device, and the color ink is ejected in a droplet form from a nozzle of the ink jet device, and is attached to a position corresponding to each pixel on the substrate. The diameter of the ink droplet ejected from the ink jet device is 5 to 100 μm, and one pixel cannot be covered by one droplet, and 3 to 20 droplets are attached to one pixel.

As an ink jet device, there are a piezo system and a bubble jet (registered trademark) system as a mechanism for ejecting ink. In addition, one or a small number of ink ejection nozzles are used to apply an electric field to ink droplets ejected from each. There are a method of controlling a landing point on a substrate and a method of providing a large number of ink ejection nozzles and depositing ink droplets on the landing point on the substrate only by positioning a nozzle corresponding to the landing point.
Although the present invention is particularly effective regardless of the type of the ink jet device, an on-demand type ink jet device that ejects ink droplets only when necessary has a large degree of freedom in color arrangement, and is preferred. As the inkjet apparatus, for example, a known apparatus described in JP-A-9-15412 and JP-A-11-209669 can be used.

The color filter of the present invention has a high color purity in one pixel, which is one colored layer of the three primary colors of red, blue, green or cyan, magenta, and yellow. Each has one or more low reflection areas. In the transmission region where light passes once, the transmittance is small instead of high color purity. On the other hand, in the reflection region where light passes twice, the color purity is set lower than the transmission region but higher. Thus, the difference between the display in the transmission mode and the display in the reflection mode can be reduced.

In the above-mentioned reflection area, a reflection film is provided on the color filter-side substrate or the counter substrate of the color filter. In the present invention, either structure can be adopted. The present invention can also be applied to a so-called COA structure in which a color filter is provided on a driving element substrate such as a TFT. In the transmission region, the reflection film is etched away by a photolithography method or the like. As the reflective film, a thin film made of aluminum or silver having a high reflectivity, or an alloy thin film mainly containing aluminum or silver can be suitably used. Further, in order to eliminate parallax, it is preferable that a reflective film is formed inside two substrates constituting the liquid crystal display element. If a reflective film is installed on the color filter side,
The color filter substrate is on the backlight side, and a colored layer is formed on the reflective film. Providing an inorganic or organic transparent protective layer above and below the reflective film for the purpose of improving corrosion resistance and the like is appropriately permitted.

It is preferable to form minute irregularities on the surface of the reflection film to scatter external light to increase the viewing angle in the reflection mode. By providing a resin layer between the reflective film and the substrate, unevenness can be provided by using a photolithography method or heat shrinkage of the resin, or unevenness can be provided by roughening the substrate surface by etching or the like.

By adjusting the size of ink droplets ejected from the ink jet device, the ink droplet ejection cycle, and the substrate feeding speed, the color purity and transmittance of the above-described transmission region and reflection region can be adjusted. In addition, there is a method in which after forming a colored layer in a transmissive area or a reflective area over the entire substrate, the color ink is changed to form a colored layer in a remaining reflective area or a transmissive area. Changing the coloring ink may be simply changing the pigment concentration, or changing the type of pigment or the combination of a plurality of pigments. This method is excellent in that the color characteristics can be set finely in the transmission area and the reflection area, and in that the thickness of the coloring layer can be made almost the same in the transmission area and the reflection area depending on the setting, but the ink exchange time loss is reduced. In order to eliminate it, one inkjet device
It is not preferable because productivity is reduced, for example, two units are required for each color. Further, a method is conceivable in which, after forming a colored layer in both the transmissive region and the reflective region under the conditions for forming the colored layer in the reflective region over the entire substrate, a colored layer is laminated only on the reflective region. Productivity is reduced due to passing through. From the viewpoint that productivity is not reduced and color mixing with adjacent pixels is easily suppressed, a method of adjusting the ejection period of the ink droplets ejected from the inkjet apparatus while keeping the substrate feeding speed constant is preferable. In the method of adjusting the ink droplet ejection cycle, the ejection cycle of the transmission region is
Preferably, it is 2/3 to 1/3 of the ejection cycle of the reflection area.

When ink droplets are ejected onto the substrate, the ink spreads on the substrate, and there is a risk that color mixing with adjacent pixels may occur. Therefore, after forming a fence with high repulsion to the colored ink in the space between the pixels, the ink mixture is applied to the pixel portion surrounded by the fence using an ink-jet device, thereby causing color mixing. Can be avoided.
When a fence with high repulsion against colored ink is provided at the boundary between the transmission area and the reflection area in one pixel, an area having a color characteristic intermediate between the transmission area and the reflection area is not generated between the transmission area and the reflection area. ,
While the display quality of the liquid crystal display element can be improved, if the colored ink repulsion fence is light-blocking, there is a problem that the aperture ratio for securing brightness decreases. In order to reduce the influence of a decrease in the aperture ratio, it is preferable to form a colored ink repelling fence in a transmission area where there is no reflective film. Conversely, when the colored ink repulsion fence is transparent, it is preferable to dispose the ink repulsion fence in the reflection area where the reflection film is provided in order to secure the transmittance of the reflection area. At this time, outside light is reflected at the ink repelling fence without passing through the coloring layer, and this light contributes to increasing the luminance while reducing the color purity of the pixel.

As such an ink-repellent fence, at least one ink-repellent resin layer or a light-shielding resin black matrix having a receding contact angle of 20 ° or more with the colored ink is formed on the surface thereof. The light-shielding resin black matrix refers to a light-shielding layer formed between pixels of a color filter, or a light-shielding layer formed between different colored stripes in a stripe-shaped colored pattern arrangement. This also plays the role of shielding the transistors and wiring portions in the active matrix drive system. The resin black matrix is formed by patterning a photosensitive or non-photosensitive resin containing a black coloring material by exposure, development or etching, or electrodeposition. The black matrix formed in this manner takes a shape such as a stripe shape, a mosaic shape, or a lattice shape corresponding to the arrangement of pixels of each of the three primary colors, and has a width of about several μm in a narrow place and about several tens of μm in a wide place. It is.

The material constituting the ink repellent barrier may be a transparent resin or a light-shielding black resin. When a black resin is used, it can also serve the function of the above-described black matrix.

According to the above method, unlike the photolithography method, patterning of pixels is not required, so that it is not necessary to include a photosensitive component in the ink.
A resin as a main component for forming a pixel and a pigment or a dye as a coloring material are included. Usually, a composition obtained by adding an appropriate amount of an ink solvent to these is used. As a coloring material, a pigment is preferable to a dye in terms of light resistance and heat resistance.

As the resin contained in the ink, a thermosetting resin having high heat resistance and high chemical resistance is used. Among them, a melamine resin which does not soften even at 200 ° C. or more,
It is preferable to use a urea resin, an alkyd resin, an epoxy resin, a phenol resin, and a cyclopentadiene resin.

The physical properties of the ink are preferably as low as possible and low in viscoelasticity. Accordingly, a high molecular weight component is not preferred as a resin component of the ink. A more effective method is to add a crosslinking component to an oligomer or a low molecular weight polymer and to crosslink with light or heat after ejection to form a resin. It is not limited to.

In order to keep the heat resistance of the color filter high, it is very effective to include the above-mentioned thermosetting resin as the resin component of the ink. It is not necessary to constitute only with resin.
Even if a small amount of these thermosetting resins is contained in the ink, the effect of improving the heat resistance is great. Further, by adding a resin other than the thermosetting resin, it is possible to prevent the color filter from cracking due to excessive curing and to improve the physical properties of the ink. The non-thermosetting resin to be added to the ink preferably has a functional group capable of undergoing a crosslinking reaction with the thermosetting resin. For example, in the case of a thermosetting resin having an OH group such as a melamine resin, a phenol resin, and an alkyd resin, a polymer containing an acrylic acid group and a methacrylic acid group, and a polymer containing an alcoholic OH group such as polyethylene glycol are preferable. The effect is observed when the proportion of the thermosetting resin contained in the ink resin is 5% or more and 100% or less, and more preferably 30% or more and 90% or less.

Examples of typical organic pigments that can be used in the coloring ink of the present invention are shown by color index (CI) numbers. Pigment Red 9, 9 as an example of a red pigment
7, 122, 123, 144, 149, 166, 16
8, 177, 190, 192, 209, 215, 21
6, 224, 254 and the like. Examples of green pigments include Pigment Green 7, 10, 36, 47 and the like. Pigment Blue 1 is an example of a blue pigment.
5: 3, 15: 4, 15: 6, 21, 22, 60, 64
And the like. Examples of yellow pigments include Pigment Yellow 12, 13, 14, 17, 20, 24, 83, and 8
6, 93, 94, 109, 110, 117, 125, 1
29, 137, 138, 139, 147, 148, 15
0, 153, 154, 166, 173 and the like. Examples of purple pigments include Pigment Violet 1
9, 23, 29, 32, 33, 36, 37, 38 and the like. Examples of orange pigments include Pigment Oranges 13, 31, 36, 38, 40, 42, 43, 51, 5
5, 59, 61, 64, 65 and the like. In addition,
Pigments that have been subjected to a surface treatment such as rosin treatment, acidic group treatment, or basic group treatment may be used as necessary.

The following means can be used for producing the ink repellent fence. Using a spin coater, blade coater, roll coater, die coater, screen printing, etc., uniformly apply a resin layer containing a component having high repellency to the colored ink on the substrate, and then heat dry or vacuum dry etc. dry. In order to make the ink repellent resin layer light-shielding, it can be realized by dispersing a black coloring material in the resin or dyeing the resin itself with a dye. In the latter case, as the black colorant dispersed in the resin layer, carbon powder having a high light-absorbing ability, and fine particles of metal oxides such as titanium, chromium, and nickel, and red,
A mixture of blue and green pigments may be blended so that a wide wavelength range can be shielded as a whole. Alternatively, a black dye can be dispersed in a resin. Further, a two-layer structure in which an ink repellent resin layer is superimposed on a light-shielding layer having no ink repellency may be employed. The following method can be used as the patterning method. First, when a photosensitive component is contained in the resin layer, an exposure mask having a fence pattern is superposed on the substrate, and UV light is irradiated from above through the mask. Thereafter, the ink is repelled only at the fence-forming portion by developing.
In this case, the mask pattern differs depending on whether the photosensitive component is a photo-curing type in which the exposed part is insolubilized or a photo-dissolving type in which the exposed part is solubilized. An exposure mask patterned so that light is transmitted only through the mask is used. In the case of the dissolution type, a pattern through which light is transmitted only through the pixel formation portion is used. When the resin layer does not contain a photosensitive component, one more photosensitive resin layer is further formed on the uniformly applied resin layer, and the photosensitive resin layer is first subjected to light patterning by the above method. Thereafter, the resin layer is patterned by wet or dry etching using the photosensitive layer as a mask. Examples of the wet etching method include a method in which the resin layer is immersed in a good solvent to dissolve the resin layer, and a method in which the resin layer is immersed in a poor solvent to swell and mechanically peel off. Further, as a dry etching method, the resin layer can be etched in an active gas or plasma. In a two-layer structure in which an ink repellent resin layer is laminated on a light-shielding layer having no ink repellency, the fact that the ink repellent resin also serves as a photoresist reduces the number of steps. The photoresist may be left in the color filter,
Although it may be peeled off, it is excellent in that the ink repellent portion disappears when the photoresist is peeled off, and the transparent protective layer, transparent conductive film or alignment layer which is laminated as necessary after the formation of the colored layer does not easily cause defects. I have. After forming a resin layer pattern having no ink repellency, the resin layer pattern can be made to have ink repellency by performing a plasma treatment in a fluorine-based gas. When wet patterning is performed, after patterning, curing is performed at 150 to 300 ° C.

As the resin constituting the ink repellent resin layer containing the photosensitive component, in the case of a photo-curing type, a polymer or an oligomer capable of forming a crosslinking point is selected as a main component, and a crosslinking agent is added thereto. realizable. If necessary, it is effective to add a reaction initiator. In particular,
The same applies to a system in which a water-soluble polymer such as gelatin, casein, polyvinyl alcohol, or polyvinylpyrrolidone is added with a crosslinking agent of ammonium dichromate or bisazide, or an aromatic polymer such as a cyclized rubber or vinyl phenol. This can be realized by a system to which a bisazide-based crosslinking agent is added.
As described above, as a system to be reacted by radical polymerization, acrylic acid, methacrylic acid or an ester group thereof is added to a low molecular weight polymer or oligomer such as polyester, epoxy, polyurethane, alkyd resin, spirane resin, and silicone resin. Can be realized by a system in which a polyfunctional acrylate or methacrylate is added as a cross-linking agent to a prepolymer into which is introduced. Further, a system in which a photocation generator is added to an epoxy resin, a system in which a methylolated melamine is added as a crosslinking agent to a phenol novolak or a polymer having an OH group, and a photoacid generator is added as an initiator. It is valid.

As the photo-solubilizing type photosensitive component, a mixture of o-naphthoquinonediazide and an alkali-soluble resin, and those obtained by ester-bonding both, can be used as the photo-solubilizing type photosensitive component. Among them, a system using a phenol novolak resin as the alkali-soluble resin is very suitable for the above purpose. In addition, a mixture of diazomeldrum acid and phenol novolak resin, a mixture of diazomedone and polyvinyl phenol, o-nitrobenzyl carboxylate and acrylic acid-methyl methacrylate
Mixtures with terpolymers and poly o-nitrobenzyl methacrylate are suitable.

The ink repellent component preferably contains, for example, atoms having a low interface energy, such as fluorine and silicon. As the repellent component containing a fluorine atom, fine particles of a polymer and an oligomer made of ethylene tetrafluoride, and as the fluorine polymer soluble in a solvent, a single polymer of vinylidene fluoride, vinyl fluoride and ethylene trifluoride is used. Copolymers, copolymers of these or ethylene tetrafluoride, and copolymers of a fluorinated monomer and another solvent-soluble monomer are suitable.

In terms of being able to be mixed with the photosensitive component in molecular order, a monomer or oligomer having both a fluorine-containing group and a hydrophilic group and / or a lipophilic group in one molecule is more preferable. As the material having the above properties, basically any material known as a fluorine-based surfactant can be applied, and the structure of a hydrophilic group or a lipophilic group is selected depending on the type of a resin as a main component. By doing so, the mixed state with the photosensitive agent can be improved.

Specific examples include a compound represented by the general formula Rf-X-Rf or (Rf-X-Rf) 2 Y (where Rf is a fluoroalkyl group, an alkylene group,
And Y; -COO -, - CONH - , - SO 2 O-,
-SO 2 NH -, - OCONH - , - OCO -, - CO
-, - OPO (OH) O -, - OSO 2 O -, - SO 2
-, -S-, -O-, -NH-, -N (R ')-, -C
ON (R') -, - OCON (R') -, - SO 2 N
In any of (R ′) −, X and Y may be the same or different. R 'represents an alkyl group. Rf may be the same or different in the molecule. )).

As a fluorine-containing group of a fluorine-based surfactant
Is CnF(2n + 1)(N = 1-50) Perfluoroal
A kill group, or one or more fluorine atoms therein
CnF (2n + 1)Branched type substituted by chain, and aromatic ring
Part or all of the hydrogen atoms of F or CnF(2n + 1)
Type and fluorine source of ethylene tetrafluoride
Child is CFThreeCan be used. Pa
-In the case of a fluoroalkyl group, its carbon chain length is not limited.
However, preferably n <20, more preferably 3 <n <1
5 is effective. As the aromatic ring type,
Benzene, difluorobenzene, trifluorobenzene,
Perfluorobenzene, fluorophenol, and
Can be used.

Such a fluorine-containing group can be present alone or in plural in the surfactant. In particular, those in which two or more terminal CF 3 — are present in the basic structural unit as the fluorine-containing component are more excellent in terms of ink repellency than those having one CF 3 — and are more preferable. Specifically, when a monomer or an oligomer is composed of a repetition of a basic structural unit, C n F is contained in the basic structural unit.
Any structure containing two or more (2n + 1) linear side chains can achieve good ink repellency.

As the hydrophilic group, OH groups, carboxylic acids, sulfonic acids, phosphoric acids and salts thereof, ammonium salts, ethylene oxide, polyethylene oxide and the like are effective. As the lipophilic group, any structure showing hydrophobicity such as a chain hydrocarbon or an aromatic ring can be used. In the case of an oligomer, a structure in which these fluorinated groups, hydrophilic groups, and lipophilic groups are pendant on the main chain is more effective.

The following method is effective as a method for forming a colored layer using an ink jet device on a substrate on which an ink repellent fence is formed by using the above method. For example, a head for three colors of red, blue, and green is prepared, and at a predetermined position other than the ink repulsion fence, a resin and a pigment are used as main components. The three primary green colored inks are ejected from the respective heads of the ink jet device to deposit the ink. afterwards,
The resin may be heat cured or light cured. A plurality of colored inks may be applied simultaneously or sequentially. It is preferable to insert a drying step after depositing one color to prevent color mixing.

In the case of forming a colored layer with an ink jet device, if ink adheres to the ink repellent fence, the amount of ink in the pixel portion becomes uneven, causing color unevenness. To prevent the ink from adhering on the fence, it is preferable that the contact angle between the fence and the ink is large. As is well known, the contact angle between a liquid and a solid has an advancing contact angle and a receding contact angle,
For the purposes of the present invention, the receding contact angle is particularly important.
To explain this point in detail, for example, if there are fine voids on the fence surface, or if there are fine irregularities on the surface, furthermore, the fence will have a component having high affinity for ink and a component having high repulsion. When both are contained, the receding contact angle may be small even though the advancing contact angle is large. In order to prevent the ink from adhering on the fence, the receding contact angle is preferably 20 ° or more. When an ink repellent fence that satisfies this condition is used, the ink can be completely pushed into the pixel portion without adhering the ink.

On the colored layer, a transparent protective layer can be formed if necessary. When the ink repelling fence is employed, it is preferable that unevenness of the color filter becomes large and a transparent protective layer is provided for flattening. Further, even when the thickness of the coloring layer is different between the transmission region and the reflection region, it is preferable to provide a transparent protective layer for flattening. By providing the transparent protective layer, elution of impurities from the coloring layer and the resin black matrix can be suppressed. As the resin used for the transparent protective layer, an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, and gelatin are preferably used. A resin having heat resistance that can withstand such heat in the manufacturing process of the display element is preferable, and a resin having resistance to an organic solvent used in the manufacturing process of the liquid crystal display element is preferable. Epoxy resins and acrylic resins are preferably used.

As a method of applying the transparent protective layer, a dip method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, and the like are preferably used as in the case of the black paste and the colored paste. ,
Heat and dry using an oven or hot plate. At this time, vacuum drying may be performed if necessary. The heating and drying conditions vary depending on the resin, solvent and paste applied amount, but are usually from 60 to 200 ° C. for from 1 to 60 minutes. The curing conditions vary depending on the resin.
1 hour to 60 minutes at 300 ° C.

The thickness of the transparent protective layer of the present invention is 0.02 μm
To 6 μm. When the thickness is less than 0.02 μm, not only is the property of blocking impurities from the black matrix and the colored layer insufficient, but also the planarization is insufficient. The thicker the transparent protective layer is, the more effective it is in reducing the step in the pixel. When the transparent protective layer is thicker than 6 μm, it is good in blocking impurities, but bubbles are apt to remain when liquid crystal is injected, and particles generated by drying the transparent protective layer produce a production yield. Is not preferred.

After forming the colored layer or the transparent protective layer, a transparent conductive film is formed if necessary. An oxide thin film such as ITO is used as the transparent conductive film.
An ITO film of about 1 μm is formed by a sputtering method or the like. In the TFT active matrix system, the transparent conductive film is a solid film in the display region. In the TFD active matrix system and the simple matrix system, the transparent conductive film is patterned into a stripe shape after forming the solid transparent conductive film. Before the formation of the transparent conductive film, a transparent inorganic film such as a silicon oxide film may be appropriately provided for the purpose of improving the adhesion to the transparent protective film and the patterning property of the transparent conductive film.

[0037]

The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto. (Measurement Method) (Method of Measuring Receding Contact Angle) An ink to be measured is filled in a micro syringe having a needle coated with Teflon (registered trademark). The needle of the microsyringe is set very close to the coated substrate to be measured. The ink to be measured is dropped on the coating so that the diameter is 1 mm or less,
The advancing contact angle between the coating and the ink is measured. At this time, the tip of the needle of the microsyringe is in a state of having entered the ink droplet. Next, the ink is gradually sucked in using a micro syringe. The ink drops on the coating become lower and at some point the diameter of the ink drops. The contact angle between the coating and the ink when the diameter starts to decrease is defined as the receding contact angle.

Example 1 (Formation of Reflection Film Pattern) A 0.2 μm aluminum film was sputtered as a reflection film on borosilicate glass. Next, after applying and drying a photoresist on the aluminum film, the reflection film pattern was exposed through a photomask. The reflective film pattern was provided with a reflection area of 85% and a transmission area of 15% in area for each of the substantially rectangular three primary colors pixels of 100 μm × 300 μm. The transmissive area was arranged such that the short side of the rectangular pixel was one side. After developing and post-baking the photoresist, the aluminum film was patterned with an aluminum etchant. (Formation of Resin Black Matrix and Colored Layer) A 0.2 wt% ethanol solution of an aminosilane-based coupling agent (PS076, Chisso) is applied on a substrate on which a reflection pattern is formed by a spinner, and then heated at 150 ° C. for 30 minutes. Heated for a minute. On this substrate, a light-shielding black resin paste comprising the following components (composition-1-1) was applied by a spinner. 8
After drying at 0 ° C. for 10 minutes, UV exposure was performed on the light-shielding layer side of the substrate through a lattice-like black matrix exposure mask. The black matrix surrounds the periphery of one substantially rectangular pixel and is also provided at the boundary between the transmissive region and the reflective region within one pixel. The line width of the black matrix around one pixel was set to 18 μm, the line width of the black matrix at the boundary between the transmission region and the reflection region was set to 10 μm, and the entire width was arranged in the transmission region. Thereafter, the substrate was immersed in a 1 wt% aqueous solution of ethanolamine to develop the black resin layer, and the black resin at the pixel portion was removed. Further, the ink was heated at 150 ° C. for 30 minutes to develop ink repellency on the surface of the black matrix. Through the above steps, a black matrix was completed.
The thickness of the black matrix was 1 μm.

Next, inks of red, green, blue and each color were prepared in the following manner (composition 1-2). First, 5 parts by weight of PR177 as a red pigment, a surfactant "Newcol"
Glass beads were added to 5 parts by weight of 710F (manufactured by Nippon Emulsifier Co., Ltd.) and 50 parts by weight of water.
After stirring for an hour, a pigment dispersion was prepared. To 64 parts by weight of the dispersion, 35 parts by weight of a melamine resin (“Sumitec Resin” M-3 manufactured by Sumitomo Chemical Co., Ltd.) and a curing agent (Sumitomo Chemical Co., Ltd.)
Was mixed with 1 part by weight of "Sumitex Accelerator" (ACX), to obtain a red ink for producing a color filter. Blue ink (using PB15: 6 as pigment) and green ink (using PG36 as pigment) were prepared in the same manner. When the receding contact angle of these inks to the ink repellent resin layer was measured, it was 50 °.

The above-described red ink was dropped on the substrate at the position of a red pixel using an ink jet device. The red coloring layer has a stripe shape, and transmission regions and reflection regions are alternately arranged in the length direction of the stripe. While moving the substrate at a constant speed in the direction of the colored layer stripe, colored ink droplets were ejected at the same pitch as the short side 82 μm of the pixel opening in the reflective area. In the transmissive area, colored ink droplets were ejected at half the pitch of the short side of the pixel opening. Next, the substrate is
C. for 15 minutes to cure the melamine component in the ink.

In the same manner as for red, ink composed of the above components was dropped at predetermined positions corresponding to blue and green pixels, and then the melamine component in the ink was cured to form pixels.
No adhesion of the ink on the black matrix was observed. (Composition 1-1) Styrene / methyl methacrylate / methacrylic acid copolymer 10 parts by weight (3/3/4) Trimethylolpropane triacrylate 4 parts by weight Epoxy acrylate 3 parts by weight Carbon black (MA100, Mitsubishi Chemical) 13 parts by weight Cumene hydroperoxide 2 parts by weight 2-butoxyethanol 80 parts by weight Fluorinated surfactant (EF-123A, Tochem Products) 5 parts by weight (F179, Dainippon Japan) Ink) 5 parts by weight (Composition-1-2) Red ink PR177 2.5 parts by weight Newcol 710F (Nippon Emulsifier Co., Ltd.) 5 parts by weight Distilled water 50 parts by weight Melamine resin (Sumitomo Chemical Co., Ltd., Sumitex resin) M-3) 35 parts by weight Curing agent (Sumitomo Chemical Co., Ltd., Accelerator ACX) 1 part by weight Blue ink PB15: 6 1 part by weight New Coal 710F (Nippon Emulsifier Co., Ltd.) 2 parts by weight Distilled water 50 parts by weight Melamine resin (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3) 40 parts by weight Curing agent (Sumitomo Chemical Co., Ltd., accelerator ACX) 2 parts by weight Part Green ink PG36 2.5 parts by weight Newcol 710F (Nippon Emulsifier Co., Ltd.) 5 parts by weight Distilled water 50 parts by weight Melamine resin (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3) 35 parts by weight Hardener (Sumitomo) 1 part by weight (Preparation of transparent protective layer and transparent conductive film) 4.08 g of methyltrimethoxysilane, 9.9 g of phenyltrimethoxysilane, and 28.8 g of γ-aminopropylmethyldiethoxysilane Dissolved in 156.3 g of γ-butyrolactone and 150 g of 3-methyl-3-methoxybutanol,
After adding 9.12 g of distilled water while stirring at 50 ° C., 50
The mixture was heated and stirred at ℃ for 2 hours to carry out hydrolysis and condensation.
Then, the temperature was raised to 130 ° C., and the alcohol and water produced were distilled off while further condensing. After cooling this solution to 50 ° C., 24.17 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added with stirring to obtain an amic acid-based polyorganosiloxane solution.

After 272 g of methyltrimethoxysilane and 396 g of phenyltrimethoxysilane were dissolved in 785.6 g of 3-methyl-3-methoxybutanol, a mixture of 3.34 g of phosphoric acid and 216 g of distilled water was added with stirring. The obtained solution was heated at 105 ° C. for 1 hour, and 302 g of a component mainly composed of methanol was distilled off. Then, the mixture was heated at 130 ° C. for 2 hours to distill off 147 g of a component mainly composed of alcohol and water. After cooling to room temperature, 86 g of 3-methyl-3-methoxybutanol was added to obtain a polyorganosiloxane solution.

650 g of ethyl acetoacetate and 3-
To a mixture of 1567 g of methyl-3-methoxybutanol was added 383 g of tetrabutoxyzirconium, and the mixture was added at 30 ° C.
After stirring for 1 hour, the mixture was left standing for 24 hours to obtain a zirconia chelate solution.

7.5 g of the above amic acid-based polyorganosiloxane solution and 10 g of the above polyorganosiloxane solution
And 1.5 g of the above chelate solution was mixed to obtain a composition for a transparent resin. The transparent resin is applied on a substrate on which a black matrix and a coloring layer of three primary colors are formed.
For 10 minutes, and then cured at 260 ° C. for 60 minutes to form a transparent protective layer having a thickness of 2 μm.

On the entire surface of the substrate on which the transparent protective layer was formed, a film was formed to a thickness of 140 nm and a surface resistance of 20 by sputtering.
An Ω / □ ITO film was formed. Next, the ITO film was patterned in a stripe shape corresponding to the pixel by a photolithography method, to obtain a color filter. (Preparation of Counter Electrode Substrate) A 140 nm thick film and a surface resistance of 2 were formed on the entire surface of the borosilicate glass substrate by sputtering.
An ITO film of 0Ω / □ was formed. Next, the ITO film was patterned in a stripe shape by photolithography so as to correspond to the pixels and to be orthogonal to the stripe pattern of the colored layer side substrate. (Preparation of Color Liquid Crystal Display Element) An alignment film having a thickness of 50 nm was printed on the color filter, dried at 80 ° C. for 10 minutes, and then cured at 180 ° C. for 60 minutes. Similarly, an alignment film was provided on the opposing substrate electrode substrate. After printing and drying an epoxy-based sealant on the periphery of the color filter substrate, the two substrates are stuck together at 150 ° C. for 3 hours.
It was fixed by heating for 0 minutes. A vacuum was evacuated between the two bonded substrates using a liquid crystal injection device, and then liquid crystal was injected from an injection port provided in a seal portion. After injecting the liquid crystal, an ultraviolet curable resin was applied to the injection port, and was sealed by irradiating ultraviolet rays. Further, a polarizing plate was attached to the outside of the substrate to produce a liquid crystal display device.

When the thus obtained color liquid crystal display device was observed in combination with an LED backlight in the transmission mode and in combination with simulated sunlight in the reflection mode, the color density of the display in the transmission mode and the color in the display in the reflection mode were observed. In the transmission mode, the color was not too light, and the visibility was good in both the transmission mode and the reflection mode.

Example 2 On a borosilicate glass substrate, the following composition (composition-2-
Applying a black resin solution having 1) with a spinner, 13
The resultant was dried by heating at 0 ° C. for 20 minutes to form a black resin layer having a thickness of 1 μm. [Composition of black resin solution] (Composition-2-1) Polyimide (Toray “Semico Fine” SP710) 30 parts by weight Carbon black (Mitsubishi Kasei MA-100) 30 parts by weight N-methylpyrrolidone 40 parts by weight Was applied with a spinner and dried by heating at 90 ° C. for 10 minutes to form a 2 μm-thick ink-repellent photosensitive resin layer. [Ink repellent photosensitive resin solution] (Composition 2-2) Positive photoresist (Tokyo Oka PMER P-6030PM-N) 63.7 parts by weight Propylene glycol monomethyl ether acetate 33.0 parts by weight Fluorinated surfactant (Tochem Products) "EFTOP" EF-123A-1) 0.3 parts by weight Fluorinated surfactant (Dainippon Ink and Chemicals "MEGAFAC" F-179) 3.0 parts by weight The ink repellent photosensitive resin layer is the same as in Example 1. UV exposure was performed through a lattice-like black matrix exposure mask. The black matrix surrounds the periphery of one substantially rectangular pixel and is also provided at the boundary between the transmissive region and the reflective region within one pixel. The line width of the black matrix around one pixel was set to 18 μm, the line width of the black matrix at the boundary between the transmission region and the reflection region was set to 10 μm, and the entire width was arranged in the transmission region.

Next, Shipley "Microposit" Deveroper /
Development was carried out with a developing solution of water = 1/5. At this time, the black resin layer was also etched simultaneously with the ink repellent photosensitive resin layer by the developer, thereby obtaining an ink repellent resin layer pattern that was laminated according to the black resin black matrix.

Then, after drying by heating at 120 ° C. for 30 minutes, the receding contact angle of the ink repellent resin layer with respect to the ink described in Example 1 was measured and found to be 72 °.

The red coloring ink described in Example 1 (composition-1-2) was dropped at the position of the red pixel where the ink repellent layer and the black resin layer were removed by using an ink jet apparatus. The red coloring layer has a stripe shape, and transmission regions and reflection regions are alternately arranged in the length direction of the stripe. While moving the substrate at a constant speed in the color layer stripe direction, in the reflection area,
Colored ink droplets were ejected at the same pitch as 82 μm on the short side of the pixel opening. In the transmissive area, colored ink droplets were ejected at half the pitch of the short side of the pixel opening. Then, the substrate is
The melamine component in the ink was cured by heating at 50 ° C. for 15 minutes.

In the same manner as for red, ink composed of the above components was dropped at predetermined positions corresponding to blue and green pixels, and then the melamine component in the ink was cured to form pixels.
No adhesion of the ink on the black matrix was observed.

Thereafter, the ink repellent resin layer was immersed in methyl cellosolve acetate to peel off the ink repellent resin layer.
Heating was performed at 0 ° C. for 30 minutes to cure the black resin black matrix. Further, in the same manner as in Example 1, a transparent protective layer and a transparent conductive film were produced. A liquid crystal display device was manufactured by laminating with a counter electrode substrate manufactured in the same manner as in Example 1. When the color liquid crystal display element thus obtained was observed in combination with the LED backlight in the transmission mode and in combination with the simulated sunlight in the reflection mode, the display density in the transmission mode and the display mode in the reflection mode were almost the same. The visibility was good in both the transmission mode and the reflection mode.

Example 3 In the same manner as in Example 2, an ink repellent resin layer and a black resin black matrix pattern were formed. The following composition-1
Using a red-colored ink No.-3, a red-colored layer in a transmission region was formed by an ink-jet apparatus in the same manner as in Example 2. Then, a colored ink was prepared using composition-1 having a lower concentration than composition-1-3
The red coloring layer in the reflection area was formed using an inkjet apparatus under the same application conditions as in the transmission area, except that the red coloring ink was changed to -2. Next, the substrate was heated at 150 ° C. for 15 minutes to cure the melamine component in the ink.

In the same manner as for red, ink composed of the components of composition-1-3 and composition-1-2 is dropped at predetermined positions corresponding to the blue and green pixels, and then the melamine component in the ink is cured. To form a pixel. No adhesion of the ink on the black matrix was observed.

Thereafter, the ink repellent resin layer was immersed in methyl cellosolve acetate to peel off the ink repellent resin layer.
Heating was performed at 0 ° C. for 30 minutes to cure the black resin black matrix.

Further, in the same manner as in Example 1, a transparent protective layer and a transparent conductive film were produced. A liquid crystal display device was manufactured by laminating with a counter electrode substrate manufactured in the same manner as in Example 1. When the color liquid crystal display element thus obtained was observed in combination with the LED backlight in the transmission mode and in combination with the simulated sunlight in the reflection mode, the display density in the transmission mode and the display mode in the reflection mode were almost the same. The visibility was good in both the transmission mode and the reflection mode. (Composition-1-3) Red ink PR177 5 parts by weight Newcol 710F (Nippon Emulsifier Co., Ltd.) 5 parts by weight Distilled water 50 parts by weight Melamine resin (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3) 35 parts by weight Curing agent (Sumitomo Chemical Co., Ltd., Accelerator ACX) 1 part by weight Blue ink PB15: 6 2 parts by weight Newcol 710F (Nippon Emulsifier Co., Ltd.) 2 parts by weight Distilled water 50 parts by weight Melamine resin (Sumitomo Chemical Co., Ltd.) Sumitex Resin M-3) 40 parts by weight Hardener (Sumitomo Chemical Co., Ltd., Accelerator ACX) 2 parts by weight Green ink PG36 5 parts by weight Newcol 710F (Nippon Emulsifier Co., Ltd.) 5 parts by weight Distilled water 50 parts by weight Melamine Resin (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3) 35 parts by weight Curing agent (Sumitomo Chemical Co., Ltd., Accelerator ACX) Part by weight Comparative Example 1 Same as Example 1 except that the colored ink droplet ejection pitch was not changed between the transmission region and the reflection region, and the colored ink droplets were ejected at the same pitch as the short side 82 μm of the pixel opening. A liquid crystal display device was manufactured.

When the thus obtained color liquid crystal display device was observed in combination with an LED backlight in the transmission mode and in combination with simulated sunlight in the reflection mode, the color was light in the transmission mode and the visibility was poor on a whitish screen. there were.

[0058]

According to the present invention, since a color filter is manufactured using an ink jet device, a color filter for a transflective color liquid crystal display device having a transmissive region and a reflective region without increasing the number of photolithography is provided.
The color purity of the colored layer in the transmissive area can be higher than the color purity of the colored layer in the reflective area, and the quality of display in a transmissive mode using a backlight as a light source and display in a reflective mode using external light as a light source. Can be reduced. For example, a display in which the color purity in the transmission mode is low and the image is whitish and has poor visibility is prevented.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA11 FB01 2H048 BA11 BA64 BB02 BB24 BB37 BB42 2H091 FA02Y FA14Y FA35Y FB08 FC01 FC02 FC25 FC29 FC30 LA11 LA13 LA15 LA16

Claims (7)

[Claims]
1. A method of manufacturing a color filter, wherein at least a colored layer is formed on a substrate by using an ink jet device, wherein the color filter has one transmission region using backlight light and one reflection region using external light. A method for manufacturing a color filter, wherein the color filter is provided in a pixel and a transmission region has higher color purity than a reflection region.
2. The method for producing a color filter according to claim 1, wherein more ink droplets are attached to the transmission area than to the reflection area.
3. The method for producing a color filter according to claim 1, wherein ink droplets having a higher density than the reflection area are attached to the transmission area.
4. An ink repellent resin layer or at least one ink repellent light-shielding resin black matrix having a receding contact angle of 20 ° or more with respect to the colored layer forming ink at a predetermined position on the substrate. Forming, and then dropping ink droplets on a predetermined portion of the substrate other than the ink repellent resin layer or the ink repellent light-shielding resin black matrix using an ink jet device to form a colored layer. A method for producing a color filter according to claim 1.
5. The color according to claim 4, wherein at least one layer of an ink-repellent resin layer or an ink-repellent light-shielding resin black matrix is formed at a boundary between a transmission area and a reflection area in one pixel. Manufacturing method of filter.
6. The method for producing a color filter according to claim 1, wherein a transparent resin layer is formed on the coloring layer.
7. A method for manufacturing a color liquid crystal display device, comprising using the color filter according to claim 1.
JP2001144631A 2001-05-15 2001-05-15 Method for manufacturing color filter and liquid crystal display element Pending JP2002341128A (en)

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Cited By (9)

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JP2005352105A (en) * 2004-06-10 2005-12-22 Toppan Printing Co Ltd Color filter and its manufacturing method
US7090950B2 (en) 2001-12-17 2006-08-15 Seiko Epson Corporation Color filter, method for making color filter, liquid crystal device, method for making liquid crystal device, and electronic apparatus
JP2006251433A (en) * 2005-03-11 2006-09-21 Toppan Printing Co Ltd Method for manufacturing substrate with black matrix, and color filter
JP2007256699A (en) * 2006-03-24 2007-10-04 Dainippon Printing Co Ltd Color filter and manufacturing method for color filter
US7336327B2 (en) 2002-08-07 2008-02-26 Seiko Epson Corporation Color filter, electro-optical device, electronic apparatus, method of manufacturing color filter substrate, and method of manufacturing electro-optical device
JP2008225303A (en) * 2007-03-15 2008-09-25 Dainippon Printing Co Ltd Color filter for translucent liquid crystal display device and manufacturing method thereof, and translucent liquid crystal display device
US7542111B2 (en) 2003-09-10 2009-06-02 Seiko Epson Corporation Color filter substrate manufacturing method
US8045103B2 (en) 2006-10-19 2011-10-25 Sharp Kabushiki Kaisha Color filter substrate and liquid crystal display device
JP5526543B2 (en) * 2006-06-20 2014-06-18 凸版印刷株式会社 Substrate with partition wall pattern and manufacturing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7090950B2 (en) 2001-12-17 2006-08-15 Seiko Epson Corporation Color filter, method for making color filter, liquid crystal device, method for making liquid crystal device, and electronic apparatus
US7336327B2 (en) 2002-08-07 2008-02-26 Seiko Epson Corporation Color filter, electro-optical device, electronic apparatus, method of manufacturing color filter substrate, and method of manufacturing electro-optical device
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JP2006251433A (en) * 2005-03-11 2006-09-21 Toppan Printing Co Ltd Method for manufacturing substrate with black matrix, and color filter
JP2007256699A (en) * 2006-03-24 2007-10-04 Dainippon Printing Co Ltd Color filter and manufacturing method for color filter
JP5526543B2 (en) * 2006-06-20 2014-06-18 凸版印刷株式会社 Substrate with partition wall pattern and manufacturing method thereof
US8045103B2 (en) 2006-10-19 2011-10-25 Sharp Kabushiki Kaisha Color filter substrate and liquid crystal display device
JP2008225303A (en) * 2007-03-15 2008-09-25 Dainippon Printing Co Ltd Color filter for translucent liquid crystal display device and manufacturing method thereof, and translucent liquid crystal display device

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