JP2003015119A - Color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter and a liquid crystal display device wherein cell gap unevenness is hardly generated even when the color filter has a transparent protective film and the difficulty of the design and the narrowness of a cell design margin which are proper to a lamination method are improved without increasing the number of manufacturing stages. SOLUTION: The color filter wherein colored layers having at least respective three primary colors and a spacer consisting of resin are provided in a screen is characterized in that the transparent protective film is formed on the colored layers and the spacer regulating the cell gap of the liquid crystal display device is formed via the transparent protective film above the part where two or three colors of colored pixels are layered.

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 in a liquid crystal display device and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art Conventionally used liquid crystal display devices are
In order to maintain the thickness (cell gap) of the liquid crystal layer, generally, plastic beads or glass fibers are provided as a spacer between the color filter substrate and an electrode substrate provided with a thin film transistor (TFT) or a plurality of scanning electrodes. The spacer member is sprayed as uniformly as possible by a dry method in which the spacer member is sprayed on the substrate or a wet method in which the spacer member is dispersed and applied in alcohol or chloroform.

The problems of this method are listed as follows: (1) When the liquid crystal penetrates, the spacer member moves and the distribution is biased, which causes unevenness in the display and causes unevenness in the display. (2) Since the position where the spacer exists cannot be controlled,
Not only the non-display portion but also the display portion, the image quality is degraded. (3) Generally, the cell gap is constantly regulated by the surface tension of the spacer and the liquid crystal and the rigidity of the glass.
If the area is larger than an inch, the cell gap becomes more uneven, which causes display unevenness. Becomes

As a method for solving these problems, forming spacers having an appropriate shape on a substrate by a photolithography method is disclosed in Japanese Patent Laid-Open Nos. 10-82909 and 1-981.
No. 0-20314 is proposed. JP-A-1
In Japanese Patent Application Laid-Open No. 0-82909 and Japanese Patent Application Laid-Open No. 10-20314, it is proposed to form the spacer with a material containing a polyimide resin, a polyvinyl alcohol resin, an acrylic resin, and a negative resist as a main component.

However, these methods still have many problems.

In the method of forming the spacer on the color filter substrate by the photolithography method, the manufacturing cost is increased because the step of applying and processing the spacer material is required in addition to the conventional color filter manufacturing step.

Further, the pillars produced by such a method are
When a negative type photosensitive acrylic resin or a positive type resist is used, the spacer is largely deformed when pressure is applied at a high temperature of about 150 ° C. when creating a panel, and cell gap unevenness due to pressure unevenness is likely to occur. Is likely to occur. This problem is particularly remarkable in a color filter having a transparent protective film. This is because a large deformation at high temperature and pressure occurs not only in the spacer but also in the transparent protective film, and this is added.

As a method which does not increase the number of manufacturing steps, JP-A-56-140324 and JP-A-63-8240.
54, JP 4-93924 A, JP 5-
In 196946, there is proposed a liquid crystal display device having a spacer having a structure in which colored layers forming a color filter are superposed.

These methods do not increase the number of steps,
Moreover, the obtained spacer has a feature that it is difficult to be crushed by pressurization at high temperature. Therefore, the above-mentioned problem does not occur, but another problem occurs. When the height of the spacer formed on the color filter substrate is changed by changing the design of the liquid crystal display device or the design of the opposing substrate, it is necessary to change the film thickness of the colored layer. In order to change the film thickness while keeping the chromaticity constant, it takes a lot of time and effort to change the material design, review the processing conditions, and evaluate the reliability.

Further, in the case of the TN method, since a transparent electrode is formed on the spacer, there is a design restriction such as a problem of short circuit with the electrode of the substrate on the opposite side.

Further, when a liquid crystal display device is manufactured by using this type of color filter, there is a problem that the design margin is narrowed because the deformation of the spacer is small.

Specifically, when the liquid crystal display device is cooled to a temperature of about -20 ° C., the liquid crystal cools and contracts, but in the liquid crystal display device having a spacer in which a colored layer is laminated, the spacer is not easily deformed. Vacuum bubbles are generated without being able to follow. On the other hand, when heated to a high temperature, the liquid crystal expands to widen the cell gap, but the elastic deformation of the spacer is small, so that it cannot follow this and gap unevenness may occur.

JP-A-11-344700 and JP-A-2
JP-A-000-89026 proposes to form a spacer on a structure in which colored layers forming a color filter are superposed. However, JP-A-11-3447
Japanese Patent Laid-Open No. 00 only describes a structure in which a transparent electrode is formed on a superposed structure and a spacer is further formed on the transparent electrode, and merely discloses improvement of the problems of the conventional spherical spacer. Absent.

Further, in Japanese Unexamined Patent Publication No. 2000-89026, it has been confirmed that the effects of the difficulty of material design, which is a problem of the laminating method, and the improvement of prevention of short circuit with the opposing substrate are effective. Points are not taken into consideration.

[0015]

The object of the color filter and the liquid crystal display device of the present invention is to solve the problem of the spherical spacer, which is likely to cause the gap unevenness, and to occur in the conventionally proposed color filter with a spacer. This was done to improve the problem.

That is, without increasing the number of manufacturing steps,
It is intended to provide a color filter and a liquid crystal display device in which cell gap unevenness is unlikely to occur even when a transparent protective film is provided, and the difficulty of design and narrow cell design margin seen in the lamination method are improved. .

[0017]

Therefore, as a result of earnest studies, the inventors of the present invention have found a color filter and a liquid crystal display device that achieve the above object. That is, the color filter, the manufacturing method thereof, and the liquid crystal display device of the present invention have the following configurations.

(1) In a color filter in which a colored layer of at least three primary colors and a spacer made of resin are provided in the screen, a transparent protective film is formed on the colored layer, and two or three colors of colored pixels are formed. A color filter characterized in that a spacer for regulating a cell gap of a liquid crystal display device is formed on the portion formed by stacking the transparent protective film through the transparent protective film.

(2) In a color filter having a colored layer of at least three primary colors and a spacer made of resin provided in the screen, a liquid crystal display device is formed on a portion formed by stacking two or three colors of colored pixels. A color filter comprising a spacer for regulating a cell gap, and a transparent protective film formed on the spacer.

(3) A transparent electrode is formed on the transparent protective film,
The color filter as described in (1) or (2) above, further comprising a spacer for regulating a cell gap formed thereon.

(4) The color filter as described in any of (1) to (3) above, wherein the spacer for controlling the cell gap is formed of a positive type resist.

(5) The color filter as described in any of (1) to (3) above, wherein the spacer for controlling the cell gap is formed of a negative resist.

(6) The color filter as described in any of (1) to (3) above, wherein the spacer for controlling the cell gap is a non-photosensitive resin.

(7) The color filter according to any one of (1) to (6) above, wherein the spacer for controlling the cell gap is formed of a resin in which a light shielding material is dispersed.

(8) The color filter as described in any one of (1) to (7) above, wherein a frame portion in which two or three colored layers are laminated is formed on the peripheral portion of the display area.

(9) A liquid crystal display device using the color filter according to any one of (1) to (8).

By forming a spacer for controlling the cell gap through a transparent protective film on a portion where two or three colors are stacked, the transparent protective film in the spacer portion can be made thinner than the display area. it can. In order for the transparent protective film to exert its effect, it is necessary to set the film thickness to a certain value or more depending on its purpose. On the other hand, when the thickness of the transparent protective film is large, the amount of deformation at the time of pressurization is large, and the cell gap unevenness is easily visible. Therefore, by providing the laminated portion below the spacer forming portion, the transparent protective film on the top of the laminated portion can flow down during coating and can be thinned. Therefore, it is possible to reduce the thickness of only the transparent protective film of the spacer portion while maintaining a constant film thickness in a necessary portion of the display region, which can improve the problem.

The same effect can be obtained by forming a spacer and then applying a transparent protective film. In this case, the effect of preventing the elution of impurities from the spacer material can be expected.

The provision of the pixel laminated portion effectively acts also in order to improve the cell gap unevenness due to the deformation of the spacer which is easily generated in the spacer formed by the conventional photolithography method. This is because the resin layer in which the pigment is dispersed has a small amount of deformation at the time of pressurization, and therefore the amount of deformation of the spacer as a whole is small. On the other hand, since it is not formed only by stacking pixels, problems such as low temperature air bubbles and cell gap unevenness at high temperatures are less likely to occur.

Further, by providing a spacer for regulating the cell gap separately from the laminated portion, it is sufficient to change only the coating film thickness of the spacer for regulating the cell gap when adjusting the cell gap, and the spacer for regulating the cell gap is used as the transparent electrode. By forming it on the upper surface, it is possible to prevent a short circuit with the counter substrate. Further, since the present invention can be easily used in combination with the technique of forming a black matrix by color superposition, by omitting the step of forming the black matrix and forming spacers for gap regulation, it is possible to improve the conventional problems without increasing the number of steps.

When the problem of increasing the number of steps is allowed, the same effect can be obtained by forming the structure of the present invention after forming the black matrix as in the case of an ordinary color filter.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

1 to 4 are schematic cross-sectional views showing an example of a color filter and a liquid crystal display device using the same.

FIG. 1 shows an example of an embodiment in which a frame portion 6 is formed by laminating colored layers 3 (3R, 3G, 3B), a transparent protective film 5 is formed, and then a spacer 4 for regulating a cell gap is formed. Is.

FIG. 2 shows an example of an embodiment in which the frame portion 6 is formed by using the black matrix 2, the transparent protective film 5 is formed, and then the spacer 4 for regulating the cell gap is formed.

FIG. 3 shows an embodiment in which a frame portion 6 is formed by laminating colored layers 3 (3R, 3G, 3B), a spacer 4 for controlling a cell gap is formed, and then a transparent protective film 5 is formed. This is an example.

In FIG. 4, after the frame portion 6 is formed by using the black matrix 2, the spacer 4 for controlling the cell gap is formed.
This is an example of an embodiment in which the transparent protective film 5 is formed after the formation of the film.

The color filter of the present invention comprises a transparent substrate 1
In addition, a colored layer 3 (3R, 3G, 3B) composed of three primary colors is applied and patterned.

As the manufacturing method, there are a photolithography method, a printing method, an electrodeposition method, an electrostatic method, an ink jet method and the like, and the photolithography method which is not particularly limited but is excellent in fine processing is particularly preferable.

The transparent substrate used in the present invention is not particularly limited, and may be made of inorganic glass such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with silica, or organic plastic. A film or sheet is preferably used.

The colored layer forming the color filter includes at least three primary colors. That is, when color display is performed by the additive method, red (R), green (G), blue (B)
In the case of performing color display by the primary color method, the three primary colors of cyan (C), magenta (M), and yellow (Y) are selected. Generally, an element including these three primary colors can be used as a unit to form a pixel for color display. For the colored layer 3, a resin colored with a colorant is used.

As the colorant used in the colored layer 3, organic pigments, inorganic pigments, dyes and the like can be preferably used, and further various additives such as an ultraviolet absorber, a dispersant and a leveling agent are added. You may. As an organic pigment,
Phthalocyanine type, azileke type, condensed azo type, quinacridone type, anthraquinone type, perylene type, perinone type and the like are preferably used.

The resin used for the colored layer 3 is preferably a photosensitive or non-photosensitive material such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, or a polyolefin resin. It is preferable to disperse or dissolve a colorant in these resins for coloring. As the photosensitive resin, there are types such as photodegradable resin, photocrosslinkable resin, and photopolymerizable resin, and in particular, a monomer having an ethylenically unsaturated bond, an oligomer or a polymer, and an initiator that generates a radical by ultraviolet rays. A photosensitive composition containing it, a photosensitive polyamic acid composition, etc. are preferably used. As the non-photosensitive resin, those that can be developed with the above-mentioned various polymers are preferably used, but the heat resistance that can withstand the heat applied in the process of forming the transparent conductive film and the process of manufacturing the liquid crystal display device. A polyimide resin is particularly preferably used, since a resin having a resistance to an organic solvent used in the manufacturing process of a liquid crystal display device is preferable.

Here, the polyimide resin is not particularly limited, but usually a polyimide precursor (n = 1) whose main component is a structural unit represented by the following general formula (I):
Those obtained by imidizing ~ 2) with heating or a suitable catalyst are preferably used.

[0045]

[Chemical 1]

In addition to the imide bond, the polyimide resin may contain a bond other than the imide bond such as an amide bond, a sulfone bond, an ether bond and a carbonyl bond.

In the above general formula (I), R1 is at least 2
It is a trivalent or tetravalent organic group having one or more carbon atoms. From the viewpoint of heat resistance, R1 is preferably a trivalent or tetravalent group containing a cyclic hydrocarbon, an aromatic or aromatic heterocycle, and having 6 to 30 carbon atoms. Examples of R1 include a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenylsulfone group, a diphenylpropane group, a benzophenone group, a biphenyltrifluoropropane group, a cyclobutyl group and a cyclopentyl group. It is not limited to these.

R2 is a divalent organic group having at least two carbon atoms, but from the viewpoint of heat resistance, R2 contains a cyclic hydrocarbon, an aromatic ring or an aromatic resin ring and has a carbon number of A divalent group of 6 to 30 is preferable. Examples of R2 include a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenylsulfone group, a diphenylpropane group, a benzophenone group, a biphenyltrifluoropropane group, a diphenylmethane group and a cyclohexylmethane group. However, it is not limited to these. The polymer having the structural unit (I) as a main component may have R1 and R2 each composed of one kind of them, or may be a copolymer composed of two or more kinds of them. Further, in order to improve the adhesiveness with the substrate, it is preferable to copolymerize bis (3-aminopropyl) tetramethyldisiloxane having a siloxane structure as a diamine component within a range that does not lower the heat resistance.

Specific examples of the polymer having the structural unit (I) as a main component include pyromellitic dianhydride, 3,3 ′, 4,
4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,
4'-biphenyltrifluoropropane tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, etc. One or more carboxylic acid dianhydride selected from paraphenylenediamine, 3,3'-diaminophenyl ether, 4,4'-diaminophenyl ether, 3,4'-diaminophenyl ether, 3,3'- Examples thereof include, but are not limited to, diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodicyclohexylmethane, and 4,4′-diaminodiphenylmethane. These polyimide precursors are known methods,
That is, it is synthesized by selectively combining tetracarboxylic acid dianhydride and diamine and reacting them in a solvent.

As a method of forming the coloring layer 3, a coloring paste in which a coloring agent is dispersed or dissolved is applied on a transparent substrate, dried, and then patterned.

As a method for dispersing or dissolving the colorant to obtain a color paste, a method of mixing the resin and the colorant in a solvent and then dispersing the mixture in a disperser such as a three-roll mill, a sand grinder or a ball mill can be used. However, the method is not particularly limited.

As a method for applying the colored paste, a dipping method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, etc. are preferably used, and thereafter, they are dried by heating using an oven or a hot plate ( Semi-cure). The semi-cure condition varies depending on the resin used, the solvent, and the amount of paste applied, but is usually 60
It is preferable to heat at ~ 200 ° C for 1 to 60 minutes.

In the case where the resin is a non-photosensitive resin, the colored paste coating film thus obtained is formed of a positive photoresist film on the resin, and then the resin is a photosensitive resin. In some cases, exposure and development are performed as they are or after forming an oxygen barrier film. If necessary, the positive photoresist or the oxygen barrier film is removed, and heat drying (main curing) is performed. This curing condition varies depending on the resin, but when a polyimide resin is obtained from a precursor, it varies slightly depending on the coating amount, but is usually 200 to 300 ° C.
It is common to heat for 1 to 60 minutes.

The above process is sequentially repeated for the three primary colors of red, blue, green or cyan, yellow and magenta to obtain a substrate in which the three primary colors are patterned on the transparent substrate.

In the black matrix layer of the present invention, two or three colors of color are overlapped in the display area, and the peripheral frame portion 6 of the display area is similarly formed of two or three colors to form a frame. It is preferably used. The black matrix layer may be formed by using metal chromium, chromium oxide, a resin in which a light shielding material is dispersed, or the like, but the number of color filter manufacturing steps is increased.

Further, the black matrix of the display section has 2
A resin in which metallic chrome, chromium oxide, and a light-shielding agent are dispersed in the peripheral frame portion 6 may be used by using a color or a color stack of three colors. In this case, the peripheral frame portion 6 is formed of a resin in which a light-shielding material is dispersed, and at the same time, a spacer for regulating the cell gap on the laminated structure portion is provided by the same material so that the number of steps is not increased and a good process is achieved. It is possible to create a color filter having a light-shielding performance for the frame portion.

The film thickness of the three primary colors is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less.
When the thickness of the colored layer is thin, it becomes difficult to obtain a predetermined chromaticity, but if this can be achieved, there is no particular limitation. on the other hand,
When the film thickness exceeds 3 μm, it becomes difficult to uniformly apply the colored layer. Especially when it exceeds 5 μm, it is difficult to dry and uneven coating is likely to occur.

After forming the three primary colors, it is desirable to form the transparent protective film 5 in order to improve flatness and prevent impurities from being eluted from the pigment into the liquid crystal 7. 3 transparent protective film
It may be formed after forming a primary color and further forming a spacer that regulates the cell gap. From the viewpoint of preventing the elution of impurities from the spacer, it is rather preferable.

As the resin used for the transparent protective film 5,
Epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, polyolefin resin, gelatin, etc. are preferably used, but the heat applied in the process of forming the transparent conductive film and the process of manufacturing the liquid crystal display device. A resin having heat resistance capable of withstanding, and a resin having resistance to an organic solvent used in a manufacturing apparatus of a liquid crystal display device are preferable. Therefore, a polyimide resin, an acrylic resin, or an epoxy resin is preferable. It is preferably used.

As a method for applying the transparent protective film 5, the dipping method,
Roll coater method, spinner method, die coating method,
A method using a wire bar or the like is preferably used, and thereafter, heat drying is performed using an oven or a hot plate. At this time, in order to improve the leveling property, vacuum drying and preliminary heating drying (semi-cure) may be performed, if necessary. The semi-cure conditions vary depending on the resin used, the solvent, and the amount of paste applied, but are usually 60 to 200 ° C.
It is preferable to heat for 60 minutes. Further, the curing conditions during heating and drying differ depending on the resin, but when a polyimide-based resin is obtained from the precursor, it slightly varies depending on the coating amount,
Generally, heating is performed at 200 to 300 ° C. for 1 to 60 minutes.

The transparent protective film 5 of the present invention has a thickness of 0.05 to
3.0 μm is desirable. A thicker layer is more effective from the viewpoint of reducing the step in the pixel, but uniform coating becomes difficult. In addition, it can be selected more suitably depending on the combination of the film thicknesses of the black matrix layer and the colored layer.

In the present invention, the physical properties such as hardness, elastic deformation amount and plastic deformation amount of the spacer defining the cell gap can be easily changed by changing the film thickness and the physical properties of the transparent protective film 5.

For example, the present invention is characterized in that the film thickness of the transparent protective film in the portion where the spacer is formed can be made smaller than the film thickness of the transparent protective film in the screen. For example, when an epoxy resin is used for the transparent protective film, it is possible to make the thickness of the display portion 1 μm and the spacer portion 0.1 μm. By providing the laminated structure of the colored layer, the transparent protective film applied to this portion flows down to the display portion, so that it can be thinned.

In the panel bonding step, the amount of deformation of the transparent protective film caused by high temperature and pressure is smaller as the film thickness is smaller. Since it is possible to reduce the film thickness of the spacer forming portion while ensuring the film thickness of the transparent protective layer required in the display portion, it is possible to obtain the effect that the necessary minimum deformation amount can be obtained.

On the contrary, when the thickness of the transparent protective film formed on the spacer portion is increased, the deformation when the spacer is loaded is larger than that when the transparent protective film is thin, but the elastic deformation of the transparent protective film is increased. Since the properties contribute, the amount of elastic deformation of the spacer as a whole also increases. As a result, the spacer elastically follows changes in the cell gap that occur when the temperature changes, etc., and it becomes easy to maintain a stable cell gap.

Further, a transparent protective film having a mechanical characteristic changed by adding an additive may be used. Examples of the additive include silica, barium sulfate, and inorganic particles.
Extender pigments such as barium carbonate, calcium carbonate and talc, ceramic powders such as alumina, zirconia, magnesia, beryllia, mullite and cordierite, and glass-ceramic composite powders are used.
Among extender pigments, barite, barium sulfate, calcium carbonate, silica and talc are preferable.

In order to change the film thickness of the transparent protective film in the portion where the spacer is formed, the viscosity and the resin concentration may be adjusted. For example, when the viscosity is increased, the transparent protective film remaining in the portion where the spacer is formed tends to be thick.

Next, if necessary, a transparent conductive film is formed.
The material for the conductive film is not particularly limited, but a material having excellent transparency is preferably used, and ITO is particularly preferably used.

The film forming method is also not particularly limited, and a vacuum deposition method, a CVD method, a sputtering method, an EB method, a material in which conductive particles are dispersed in a resin such as polyimide, a black paste,
As in the case of the colored paste, a dipping method, a roll coater method, a spinner method, a die coating method, a method of coating with a wire bar, a method of heat treatment, etc. are preferably used.

Finally, the spacer 4 for controlling the cell gap is formed.

As the resin used for forming the spacer, a resin itself having photosensitivity or a non-photosensitive resin may be used.

As the photosensitive resin, either a positive type or a negative type photosensitive resin may be used, but it can be selected in consideration of required mechanical strength and the like.

The positive resist is not particularly limited, but a mixture of novolac resin and naphthoquinonediadisulfonic acid ester is preferably used.

Examples of the negative resist include cyclized rubber-bisazide type, phenol resin-azide type, acrylic resin, and chemical sensitization type. For example, in the case of acrylic type resin, an oligomer having a molecular weight of 1000 to 2000 is preferably used. Examples thereof include polyester acrylate, epoxy acrylate such as phenol novolac epoxy acrylate, o-cresol novolac epoxy acrylate, polyurethane acrylate, polyether acrylate, oligomer acrylate, alkyd acrylate, and melamine acrylate. As the polymerizable acrylate monomer, 1,4-butanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate , Pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol acrylate, dipentaerythritol hexaacrylate.

Further, when the desired mechanical properties cannot be satisfied only by the above-mentioned resins, various additives may be added to the resin for adjustment. As the additives, for example, in inorganic particles, silica, barium sulfate, barium carbonate, calcium carbonate, extender pigments such as talc, and coloring pigments such as black, red, blue, green, and alumina, zirconia, magnesia, beryllia, Ceramic powders such as mullite and cordierite, and glass-ceramic composite powders are used. Among extender pigments, barite, barium sulfate, calcium carbonate, silica and talc are preferable.

As a method of forming the spacer 4, for example, there is a method of applying a resin on a substrate and drying it, and then patterning the resin. Like the colored layer, the resin coating method includes a dip method, a roll coater method, a spinner method, a die coating method, and a method using a wire bar. From the viewpoint of forming a uniform height, the die coating method is used. Method is preferred. After that, vacuum drying may be performed and heating may be further performed using an oven or a hot plate.

The spacer 4 thus obtained is then exposed and developed and heated again. At this time, the exposure amount varies depending on the film thickness of the resin, the area of the spacer, and the like.

In the case of a positive type photoresist, the exposure amount is 6
0 to 300 mj / cm ² is preferable, and more preferably 8
It is 0 to 160 mj / cm ² . Also, the developer concentration varies depending on the shape, height and area of the spacer, but is 0.5 to 3
% Is more preferable, more preferably 1 to 2.5%, and further preferably 2 to 2.4%.

In the case of a negative type photoresist, the exposure amount is 6
0 to 500 mj / cm ² is preferable, and 10 is more preferable.
It is 0 to 300 mj / cm ² . The developer concentration is preferably 0.05 to 3%, more preferably 0.1 to 1
%.

After that, it is reheated in an oven or a hot plate to complete the curing. The reheating temperature may be appropriately selected depending on the type of resin used, but when a polyimide resin is used, for example, the temperature is preferably 180 to 300 ° C, more preferably 250 to 290 ° C. is there. When an acrylic resin is used, preferably 1
It is in the range of 80 to 290 ° C, and more preferably 220 to
It is in the range of 250 ° C.

The resin used is not particularly limited, but materials such as epoxy resins, acrylic resins, urethane resins, polyester resins, polyimide resins, polyolefin resins and the like are preferably used.

Further, when the desired mechanical properties cannot be satisfied only by the above-mentioned resins, various additives may be added to the resin for adjustment. As the additives, for example, in inorganic particles, silica, barium sulfate, barium carbonate, calcium carbonate, extender pigments such as talc, and coloring pigments such as black, red, blue, green, and alumina, zirconia, magnesia, beryllia, Ceramic powders such as mullite and cordierite, and glass-ceramic composite powders are used. Among extender pigments, barite, barium sulfate, calcium carbonate, silica and talc are preferable.

As a method of forming the spacer 4 using a non-photosensitive resin, for example, there is a method of applying a resin on a substrate and drying the resin, followed by patterning. As a method of applying the resin, similar to the coloring layer, a dipping method,
A roll coater method, a spinner method, a die coating method, a method using a wire bar and the like are available, but the die coating method is preferable from the viewpoint of forming a shape having a uniform height. After that, vacuum drying may be performed and heating may be further performed using an oven or a hot plate.

The non-photosensitive resin film thus obtained is subjected to exposure and development after forming a positive photoresist film thereon. If necessary, the positive photoresist is removed and heat-dried (main curing). The curing conditions vary depending on the resin, but when a polyimide-based resin is obtained from the precursor, the curing condition varies slightly depending on the coating amount, but it is generally heating at 200 to 300 ° C. for 1 to 60 minutes.

Further, it is also preferable that a resin in which a light shielding agent is dispersed is used for the spacer 4 regardless of whether it is photosensitive or non-photosensitive.

The resin used is not particularly limited, but materials such as epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, and polyolefin resin are preferably used.

As the light-shielding agent, carbon black, titanium oxide, metal oxide powder such as iron tetraoxide, metal sulfide powder,
In addition to the metal powder, a mixture of red, blue, and green pigments can be used.

Since it is formed on the uppermost layer of the color filter, a suitable light shielding agent differs depending on the required electrical characteristics.

The method of forming the spacers using the resin in which the light-shielding agent is dispersed is the same as in the case of the above-mentioned photosensitive and non-photosensitive resins.

It is also possible to use the resin containing the light-shielding agent to form the spacers and simultaneously use the spacers for the frame 6 at the peripheral portion of the display portion. In this case, the film thickness is preferably 0.5 μm
It is 2 μm, more preferably 1 μm to 1.5 μm. If the film thickness is less than 0.5 μm, the light-shielding property becomes insufficient, which is not preferable. On the other hand, the film thickness is 1.5μ
If the thickness is thicker than m, a residue is likely to remain in the screen, which causes a decrease in transmittance. However, the primary purpose of forming the present resin film is to use it as a spacer, and the film thickness is determined by the height of the spacer. Therefore, the peripheral frame portion 6 may be formed by being overlapped with a blue pixel or the like, if necessary.

The shape of the spacer is not particularly limited, and may be appropriately selected from circles, ellipses, ellipses, squares, rectangles, triangles, and other polygons.

The size of the spacer is also not particularly limited. If there is too much area, it may cause low temperature foaming,
On the other hand, if it is small, the spacers are likely to be crushed and unevenness in the gap is likely to occur. The proper size depends on the design of the panel and the manufacturing conditions of the panel, but if it is circular, it is 10 μmφ ~
20 μmφ is desirable.

The spacer may be formed before forming the transparent protective film. In this case, there is an effect of preventing the elution of impurities from the spacer material.

Next, the liquid crystal display device of the present invention will be described.

A known technique is used for the method of manufacturing the array substrate 8 and the panel.

The present invention does not particularly limit the driving method of the liquid crystal display device and the liquid crystal alignment method. However, the effect is particularly exerted in a mode using a lateral electric field method or a viewing angle widening film in which unevenness in cell thickness is sharply displayed. Further, a liquid crystal display device using a low-voltage driven liquid crystal for which a transparent protective film is highly necessary because it is easily affected by impurities, and a liquid crystal display device with a narrow cell gap of 3.5 μm or less that requires excellent flatness, The STN method which requires excellent flatness is also effective.

[0097]

EXAMPLES The present invention will be described in more detail based on the following preferred examples, but the effects of the present invention are not limited by the following examples.

Example 1 (Formation of Colored Layer) Glass Substrate (Corning # 173)
7) Apply the red paste on top with a curtain flow coater,
It was dried on a hot plate at 130 ° C. for 10 minutes to form a blue resin coating film. Thereafter, a positive photoresist (manufactured by Shipley, SRC-100) was applied by a reverse roll coater, and prebaked at 100 ° C. for 5 minutes on a hot plate,
After mask exposure by irradiating ultraviolet rays of 100 mj / cm ² using an ultra-high pressure mercury lamp, a 2.25% tetramethylammonium hydroxide aqueous solution is used to simultaneously develop the photoresist and etch the resin coating film to form a pattern. Formation, resist stripping with methyl cellosolve acetate,
It was imidized by heating at 300 ° C. for 10 minutes on a hot plate to form a blue colored layer. The film thickness of the blue colored layer was measured and found to be 1.7 μm.

Similarly, after washing with water, a red paste was applied to a substrate having a blue colored layer formed on a glass substrate and patterned to form a red colored layer. The thickness of the red colored layer was measured and found to be 1.7 μm.

An overlap of 4 μm was provided between the blue pixel and the red pixel, and a laminated structure of blue and red was formed in a portion where a spacer is formed later.

Further, after washing with water, the glass substrate was blue,
A green paste was applied onto the substrate on which the red-green colored layer was formed and patterned to form a green colored layer. The film thickness at the opening of the green colored layer was measured and found to be 1.7 μm.

Between blue and green, and between red and green are 5 μm and 6 respectively.
The overlap was μm. Further, the portion forming the spacer has a laminated structure of three colors of blue, red and green, and the frame of the peripheral portion of the display portion has a laminated structure of two colors of blue and red.

At this stage, the height to the top of the laminated portion where the spacer is installed was measured to be 5.2 μm, and the frame portion was 3.4.
was μm. In addition, the optical density of the frame portion was measured and found to be 3.5, indicating that there was a sufficient light-shielding property. (Formation of transparent protective film) After that, an epoxy resin solution is applied by a curtain flow coater, and a hot plate is used for 28 times.
A transparent protective film was formed by heating at 0 ° C. for 10 minutes. The thickness of the raw glass portion was measured and found to be 1.0 μm.

At this stage, the height from the surface of the glass substrate to the top of the laminated portion on which the spacer is installed is measured to be 5.3 μm.
It was confirmed that the transparent protective film was laminated only 0.1 μm on this portion. On the other hand, the film thickness of the frame portion was 4.4 μm, and here the layers were laminated by 1 μm. (Formation of spacer) Photosensitive acrylic resin Optoma NN
-810 (manufactured by JSR) was applied with a curtain flow coater, and vacuum drying was performed while heating at 80 ° C. Furthermore, after performing mask exposure by irradiating 300 mj / cm ² ultraviolet rays using a high pressure mercury lamp, development was performed using a 0.4% tetramethylammonium hydroxide aqueous solution, and heating was performed on a hot plate at 240 ° C. for 10 minutes, The reaction was completed.

The spacer height of the manufactured color filter was measured with a contact surface profilometer. The height from the surface of the glass substrate to the top of the spacer was 6.8 μm in the display region and 6.6 μm on the peripheral frame. The film thickness of the G part including the transparent protective film was 2.8 μm, and the height from the pixel surface to the top of the spacer was 4.0 μm. The shape of the spacer is a cylinder, and the size of the top is 20 μmφ.
Met. (Production of liquid crystal display device) After applying and heating a polyimide-based alignment film on a color filter substrate, a rubbing treatment is performed,
Similarly, an alignment film was formed and a rubbing-processed TFT was attached to a substrate provided with comb-teeth-shaped electrodes using a sealant. Next, a liquid crystal was injected from an injection port provided in the seal portion, the liquid crystal was injected, the injection port was sealed, and an optical film such as a polarizing plate was attached to obtain a horizontal electric field type liquid crystal display device. (Evaluation of Liquid Crystal Display Device) The cell gap of the manufactured liquid crystal display device was measured by Otsuka Electronics Cell Gap Measuring Device RETS-3.
As a result of measurement at 000, the average was 4.0 μm. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, there was no gap unevenness and it was uniform. Using this liquid crystal display device, low temperature foaming and gap unevenness at high temperature were evaluated. The low temperature foaming evaluation was carried out by leaving it in an environment of −20 ° C. for 24 hours and confirming the presence or absence of vacuum foam. The evaluation of the gap unevenness at a high temperature was performed by standing the liquid crystal display device at 50 ° C. and observing. As a result, low-temperature foaming did not occur, and gap unevenness at high temperatures was within the allowable range.

(Example 2) (Production of color filter) After forming a colored layer in the same manner as in Example 1, a spacer was produced first, and then a transparent protective film was formed. The spacer height of the manufactured color filter was measured with a contact surface profilometer. The height from the surface of the glass substrate to the top of the spacer was 6.8 μm in the display region and 6.4 μm on the peripheral frame. The film thickness of the G part including the transparent protective film was 2.8 μm, and the height from the pixel surface to the top of the spacer was 4.0 μm. The shape of the spacer was a cylinder, and the size of the top was 20 μmφ in diameter. (Production of Liquid Crystal Display Device) A horizontal electric field type liquid crystal display device was produced in the same manner as in Example 1. (Evaluation of Liquid Crystal Display Device) A liquid crystal display device manufactured in the same manner as in Example 1 was evaluated. Cell gap is 4.0 on average
was μm. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, there was no gap unevenness and it was uniform. As a result of evaluation of low-temperature foaming and gap unevenness at high temperature, low-temperature foaming did not occur, and gap unevenness at high temperature was within an allowable range.

Example 3 In Example 1, after forming the transparent protective film, the transparent electrode was formed. At that time, a metal mask was attached on the transparent protective film, and ITO was formed in the display region by a sputtering method. ITO film thickness is 1
At 50 nm, the surface resistance was 17Ω / □. After this,
A spacer was formed in the same manner as in Example 1. The height from the pixel surface of the formed color filter to the top of the spacer was 4.0 μm, which was the same as in Example 1. (Production of Liquid Crystal Display Device) A liquid crystal display device was produced in the same manner as in Example 1. At this time, the substrate on the array side corresponds to TN driving, and electrodes are formed for each pixel. When laminating the polarizing plates, two types were prepared, one with a viewing angle widening film and one without. (Evaluation of Liquid Crystal Display Device) The cell gap of the liquid crystal display device thus prepared was measured by Otsuka Electronics Cell Gap Measuring Device RETS-3.
The result of measurement at 000 was 4.3 μm on average. The difference in cell thickness from Example 1 is due to the difference in the structure of the array substrate. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, it was found that there was no gap unevenness and that the film was uniform regardless of the presence or absence of the viewing angle widening film. In the same manner as in Example 1, low-temperature foaming and cell gap unevenness at high temperature were evaluated. As a result, there was no low-temperature foaming and the gap unevenness at high temperatures was within the allowable range.

(Example 4) In Example 1, a positive resist was used as the spacer material. As a positive resist, a photoresist SRC-100 manufactured by Shipley Co., Ltd.
Was used. Photoresist SRC-100 is applied with a curtain flow coater, and hot plate is applied at 100 ° C for 1
Heated for 0 minutes. Next, using a high pressure mercury lamp,
After mask exposure by irradiating j / cm ² ultraviolet rays,
Develop with a 2.25% tetramethylammonium hydroxide aqueous solution, and use a hot plate at 240 ° C. for 10
Heated for a minute to complete the reaction. The spacer height of the manufactured color filter was measured with a contact surface profilometer. The height from the glass substrate surface was 6.8 μm in the display area and 6.0 μm on the peripheral frame. The film thickness of the G part including the transparent protective film was 2.8 μm, and the height from the pixel surface to the top of the spacer was 4.0 μm. The shape of the spacer is a cylinder, and the size of the top is 16 μmφ
Met. (Production and Evaluation of Liquid Crystal Display Device) A horizontal electric field type liquid crystal display device was produced in the same manner as in Example 1. The cell gap of the manufactured liquid crystal display device was measured by a cell gap measuring device RETS-3000 manufactured by Otsuka Electronics, and as a result, the average was 3.9 μm.
It was m. The difference in cell thickness from Example 1 is due to the difference in the structure of the array substrate. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, there was no gap unevenness and it was uniform. In the same manner as in Example 1, low-temperature foaming and cell gap unevenness at high temperature were evaluated. As a result, there is no low temperature foaming,
Further, the gap unevenness at high temperature was within the allowable range.

(Example 5) In Example 1, a resin in which a light-shielding agent was dispersed was used as the spacer material. A black paste in which titanium oxynitride was dispersed in a polyimide resin was applied with a curtain flow coater, and heated and dried at 130 ° C. for 10 minutes on a hot plate. A positive photoresist (manufactured by Shipley, SRC-100) is applied by a curtain flow coater, and a hot plate is applied at 100 ° C. for 5
Pre-bake for 100 minutes / 100mj / using an ultra-high pressure mercury lamp
cm ² After mask exposure by UV irradiation, using a 2.25% aqueous solution of tetramethylammonium hydroxide, develop the photoresist and etch the resin coating at the same time to form a pattern, and strip the resist with methyl cellosolve acetate. Then, on a hot plate at 300 ℃, 10
The spacer was completed by imidizing by heating for a minute. The spacer height of the prepared color filter was measured with a contact type surface profilometer. The height from the surface of the glass substrate was 6.8 μm in the display region and 5.2 μm on the peripheral frame. The film thickness of the G part is 2.8 including the transparent protective film.
The height from the pixel surface to the top of the spacer was 4.0 μm. The shape of the spacer was a cylinder, and the size of the top was 16 μmφ in diameter. (Production and Evaluation of Liquid Crystal Display Device) In the same manner as in Example 1, a horizontal electric field type liquid crystal display device was produced. The cell gap of the manufactured liquid crystal display device was measured by a cell gap measuring device RETS-3000 manufactured by Otsuka Electronics, and as a result, an average of 4.0 μm.
It was m.

As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, it was found that there was no gap unevenness and that it was uniform.

(Example 6) In Example 5, the frame at the peripheral portion of the display area was used as a spacer material, and a resin in which a light shielding agent was dispersed was used as a spacer material. At the time of forming the colored layer, only the pattern of the display region was formed, and the frame portion was not formed by stacking. A frame portion was created at the same time when the spacer was formed. The film thickness of the frame is 1.8
was μm. The spacer height of the manufactured color filter was measured with a contact surface profilometer. The height from the surface of the glass substrate was 6.8 μm in the display area, and no column was provided in the peripheral frame portion. The height from the surface of the G pixel to the top of the spacer was 4.0 μm. The shape of the spacer was a cylinder, and the size of the top was 16 μmφ in diameter. (Production and Evaluation of Liquid Crystal Display Device) A horizontal electric field type liquid crystal display device was produced in the same manner as in Example 1. The cell gap of the manufactured liquid crystal display device was measured by a cell gap measuring device RETS-3000 manufactured by Otsuka Electronics, and as a result, an average of 4.0 μm.
It was m. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, there was no gap unevenness and it was uniform.

(Example 7) In Example 1, a transparent protective film was formed by using, as the transparent protective film, a liquid having an increased solid content concentration and viscosity of an epoxy resin solution. The thickness of the raw glass portion was measured and found to be 1 μm. The transparent protective film laminated on the spacer portion had a thickness of 0.4 μm.

Thereafter, the spacers were formed in the same manner as in Example 1 so that the height from the surface of the color filter pixel to the top of the spacer was 4.0 μm, which is the same as in Example 1. (Production and Evaluation of Liquid Crystal Display Device) A horizontal electrolysis type liquid crystal display device was produced in the same manner as in Example 1. The cell gap of the produced liquid crystal display device was measured by a cell gap measuring device RTS-3000 manufactured by Otsuka Electronics Co., Ltd., and as a result, the average was 4.0 μm. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, there was no gap unevenness and it was uniform.

Example 8 In Example 7, the transparent protective film was formed so that the film thickness of the raw glass portion of the transparent protective film was 1.5 μm. The transparent protective film laminated on the spacer portion had a thickness of 0.6 μm.

Thereafter, as in Example 1, spacers were formed so that the height from the color filter pixel surface to the spacer top was 4.0 μm, which is the same as in Example 1. (Production and Evaluation of Liquid Crystal Display Device) A horizontal electrolysis type liquid crystal display device was produced in the same manner as in Example 1. The cell gap of the produced liquid crystal display device was measured by a cell gap measuring device RTS-3000 manufactured by Otsuka Electronics Co., Ltd., and as a result, the average was 4.0 μm. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, there was no gap unevenness and it was uniform.

Comparative Example 1 A color filter was prepared in the same manner as in Example 1 except that the laminated portion was not provided below the spacer forming portion. Since the laminated portion was not provided, by increasing the thickness of the spacer coating, the height from the transparent protective film surface of the G pixel to the top of the spacer could be 4.2 μm as in Example 1.

A liquid crystal display device was similarly prepared and evaluated. As a result, the cell gap could be set to 4.0 μm as in Example 1, but thin gap unevenness could be confirmed by visual observation. This unevenness reflected the unevenness at the time of heating / pressurizing in the panel manufacturing process.

(Comparative Example 2) A color filter was prepared in the same manner as in Example 3 except that the laminated portion was not provided below the spacer forming portion. Similarly, as a result of making and evaluating a TN type liquid crystal display device, a very slight gap unevenness can be confirmed in the panel not using the viewing angle widening film, and this unevenness is more noticeable in the panel using the viewing angle widening film. Was given.

(Comparative Example 3) In Example 1, the spacer was formed only by stacking the colored layers with the colored layer having a thickness of 2.3 μm. After attaching the transparent protective film, the height was measured in the same manner as in Example 1. The height from the surface of the G pixel to the top of the spacer was 4.2 μm. A lateral electrolysis type liquid crystal display device was prepared using this color filter, and the cell gap was measured and found to be 4.2 μm. Gap unevenness was confirmed by visual inspection, but no unevenness was observed.

As in Example 1, low temperature foaming and gap unevenness during heating were observed. As a result, low-temperature foaming was confirmed, and display unevenness due to gap unevenness was confirmed near the lower side of the cell, the extent of which exceeded the allowable range.

Comparative Example 4 In Example 1, after the colored layers of three colors were laminated, an acrylic photosensitive resin was laminated on the laminated colored layers without coating and forming a transparent protective film to form a spacer. Formed. The height from the surface of the G pixel to the top of the spacer was 4.0 μm. Using this color filter, a lateral electrolysis type liquid crystal legal device was prepared and the cell gap was measured. As a result, it was 4.0 μm. No gap unevenness could be confirmed by visual inspection.

As in Example 1, low-temperature foaming and gap unevenness during heating were observed. As a result, low-temperature foaming was confirmed, and display unevenness due to gap unevenness was slightly confirmed at the lower side of the cell.

(Example 9) (Preparation of Black Matrix Layer) A black paste in which carbon black was dispersed was applied onto a glass substrate (# 1737 manufactured by Corning) using a curtain flow coater and dried at 130 ° C. for 10 minutes on a hot plate. , A black resin coating film was formed. After this, a positive photoresist (made by Shipley, S
RC-100) was applied by a reverse roll coater, prebaked at 100 ° C. for 5 minutes on a hot plate, masked by ultraviolet irradiation of 100 mj / cm ² using an ultrahigh pressure mercury lamp, and then 2.25% tetramethylammonium hydroxy. The photoresist is developed and the resin coating film is etched at the same time using an aqueous solution of water, a pattern is formed, the resist is stripped off with methyl cellosolve acetate, and heated on a hot plate at 300 ° C. for 10 minutes for imidization,
A black matrix layer was formed. The film thickness of the black matrix layer was measured and found to be 1.2 μm. (Production of Colored Layer) A blue paste was applied to a substrate on which a black matrix had been formed by a curtain flow coater and dried at 130 ° C. for 10 minutes to form a blue resin coating film. After that, a positive photoresist (manufactured by Shipley, SRC-100) is applied by a reverse roll coater,
After prebaking at 100 ° C. for 5 minutes on a hot plate and mask exposure by irradiating 100 mj / cm ² ultraviolet rays using an ultra-high pressure mercury lamp, the photoresist was developed using a 2.25% tetramethylammonium hydroxide aqueous solution. The resin coating film was simultaneously etched to form a pattern, the resist was stripped off with methyl cellosolve acetate, and the film was heated on a hot plate at 300 ° C. for 10 minutes for imidization to form a blue stripe pattern on the black matrix layer. The thickness of the blue pattern opening is 1.
It was 7 μm. Similarly, red and green patterns were formed. The red and green film thicknesses were measured and found to be 1.7μ
It was m. As in Example 1, a red pattern was provided on the blue stripe BM where spacers were formed. The height from this glass substrate to the top of the laminated part is 4.5μ.
It was m. (Formation of transparent protective film) After that, an epoxy resin solution is applied by a curtain flow coater, and a hot plate is used for 28 times.
A transparent protective film was formed by heating at 0 ° C. for 10 minutes. The thickness of the raw glass portion was measured and found to be 1.0 μm. At this stage, the height from the surface of the glass substrate to the top of the laminated portion where the spacer is installed was measured to be 4.6 μm, and it was confirmed that the transparent protective film was laminated only 0.1 μm in this portion. (Formation of spacer) Photosensitive acrylic resin Optoma NN
-810 (manufactured by JSR) was applied with a curtain flow coater, and vacuum drying was performed while heating at 80 ° C. Furthermore, after performing mask exposure by irradiating 300 mj / cm ² ultraviolet rays using a high pressure mercury lamp, development was performed using a 0.4% tetramethylammonium hydroxide aqueous solution, and heating was performed on a hot plate at 240 ° C. for 10 minutes, The reaction was completed.

The spacer height of the manufactured color filter was measured with a contact surface profilometer. The height from the surface of the glass substrate to the top of the spacer was 6.8 μm in the display region and 6.6 μm on the peripheral frame. The film thickness of the G part including the transparent protective film was 2.8 μm, and the height from the pixel surface to the top of the spacer was 4.0 μm. (Production of Liquid Crystal Display Device) A horizontal electric field type liquid crystal display device was produced in the same manner as in Example 1. (Evaluation of Liquid Crystal Display Device) A liquid crystal display device manufactured in the same manner as in Example 1 was evaluated. Cell gap is 4.0 on average
was μm. As a result of visual observation of this liquid crystal display device in a non-lighted state and a lighted state, there was no gap unevenness and it was uniform. As a result of evaluation of low-temperature foaming and gap unevenness at high temperature, low-temperature foaming did not occur, and gap unevenness at high temperature was within an allowable range.

Example 10 The hardness of the spacer material used in Examples and Comparative Examples was measured. The measurement was performed using Fisherscope H-100. The measurement is
(1) Three-color laminated portion of blue, red, and green described in Example 1,
(2) The acrylic photosensitive resin single layer described in Example 1 was used, and (3) the three-color laminate + acrylic photosensitive resin + transparent protective film described in Example 1 were used.

Using a flat plate indenter of 100 μmφ, a predetermined load was applied for 5 seconds, holding for 2 seconds, and unloading for 2 seconds. The evaluation results are shown in Table 1.

[0127]

[Table 1]

When the same load is applied, the deformation amount is in the order of the three-color laminated portion <Example 2 <acrylic, and the characteristic between the characteristic of the acrylic material having a large amount of deformation and the characteristic of the three-color laminated portion is shown. I was able to get it.

Example 11 The hardness of the spacer manufactured in the example was measured to verify the physical properties of the spacer when the thickness of the transparent protective film was changed. The measurement device was a Fisherscope H-100. The measurement is
(1) Three-color laminate shown in Example 1 + transparent protective film + acrylic photosensitive resin, (2) Three-color laminate shown in Example 7 + transparent protective film + acrylic photosensitive resin, (3) Example 8 (3) Laminated layer + transparent protective film + acrylic photosensitive resin, and (4) Three-colored laminate shown in Comparative Example 4 + acrylic photosensitive resin.

Using a flat plate indenter of 100 μmφ, a predetermined load was applied for 5 seconds, then held for 2 seconds, and unloaded for 2 seconds. The measurement was carried out at sample temperatures of 25 ° C and 150 ° C. The evaluation results are shown in Table 2.

[0131]

[Table 2]

At 25 ° C., 10 m on each spacer
The amount of deformation under N load was in the order of Comparative Example 4 <Example 1 <Example 7 <Example 8, and it was confirmed that the amount of deformation can be adjusted by the thickness of the transparent protective film that fits the spacer height.
The residual deformation amount of the spacer at the time of unloading, that is, the plastic deformation amount is in the order of Example 8 <Example 7 <Example 1 <Comparative Example 4, and the elastic deformation amount of the transparent protective film is the elastic deformation amount of the spacer itself. It was confirmed that it contributed greatly.

At 150 ° C., the amount of deformation during loading and unloading is in the same order as at 25 ° C., and even at high temperature, the elastic deformation amount of the transparent protective film greatly contributes to the elastic deformation amount of the spacer itself. I was able to confirm.

[0134]

By providing the laminated structure of the colored layer in the spacer forming portion of the color filter, it is possible to reduce the thickness of the transparent protective film in the spacer portion. The deformation of the transparent protective film can be reduced, and the liquid crystal cell gap can be made uniform.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a color filter for a liquid crystal display device of the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of the color filter for a liquid crystal display device of the present invention.

FIG. 3 is a schematic cross-sectional view showing another example of the color filter for a liquid crystal display device of the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of the color filter for a liquid crystal display device of the present invention.

[Explanation of symbols]

1 ... Transparent substrate 2 ... Black matrix 3R: red colored layer 3G: green colored layer 3B ... Blue colored layer 4 ... Spacer 5: Transparent protective film 6 rim frame part 7 ... Liquid crystal 8 ・ ・ ・ Array substrate

Continued front page    (72) Inventor Tomohiko Hatano             1-1 1-1 Sonoyama, Otsu City, Shiga Prefecture Toray Co., Ltd.             Ceremony company Shiga business site F-term (reference) 2H048 BA45 BA48 BB02 BB03 BB07                       BB08 BB37 BB42                 2H089 HA15 JA07 LA01 LA11 NA12                       QA14 TA12                 2H091 FA02Y FA34Y FB02 FD04                       FD06 GA01 GA16 LA13 LA16

Claims (9)

[Claims] 1. A color filter in which a colored layer for each of at least three primary colors and a spacer made of a resin are provided in a screen, and a transparent protective film is formed on the colored layer so that two or three colors of colored pixels are formed. A color filter characterized in that a spacer for regulating a cell gap of a liquid crystal display device is formed on the stacked portion through the transparent protective film. 2. A cell of a liquid crystal display device in a color filter having a colored layer of at least three primary colors and a spacer made of resin provided in a screen, on a portion formed by stacking two or three colors of colored pixels. A color filter comprising a spacer for controlling a gap, and a transparent protective film formed on the spacer. 3. The color filter according to claim 1, wherein a transparent electrode is formed on the transparent protective film, and a spacer for regulating a cell gap is further formed on the transparent electrode. 4. The color filter according to claim 1, wherein the spacer for controlling the cell gap is formed of a positive type resist. 5. The color filter according to claim 1, wherein the spacer for controlling the cell gap is formed of a negative resist. 6. The color filter according to claim 1, wherein the spacer that regulates the cell gap is a non-photosensitive resin. 7. The color filter according to claim 1, wherein the spacer for controlling the cell gap is formed of a resin in which a light shielding material is dispersed. 8. A colored layer of two colors or three is provided on the peripheral portion of the display area.
The color filter according to any one of claims 1 to 7, wherein a frame portion in which colors are laminated is formed. 9. A liquid crystal display device using the color filter according to any one of claims 1 to 8.