JPH10104640A - Substrate for liquid crystal display element and color liquid crystal display element including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for a liquid crystal display element which embodies a sufficient cell gap, maintains the uniform cell gap within an image plane and is more hardly degraded in its display grade than the conventional elements when the force or impact from outside is applied thereon and a color liquid crystal display element including this substrate. SOLUTION: This substrate for the liquid crystal display element has the spacers fixed in the non-display region on the substrate. The elastic restoration rate of the spacers to a compressive stress of 0.4 to 0.6GPa is 20 to 80%. The substrate has the spacers contg. the acrylic resins fixed to the non-display region on the substrate for the liquid crystal display element and the elastic restoration rate of the spacers to the compressive stress of 0.4 to 0.6GPa is 0.01 to 80%. Further, at least one substrate for the liquid crystal display element of the color liquid crystal display element formed by holding the liquid crystal layer with two sheets of the substrates for the liquid crystal display element is the substrate for the liquid crystal display element described above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display device substrate having a spacer function and a color liquid crystal display device including the same.

[0002]

2. Description of the Related Art Conventionally, a liquid crystal display device generally employs plastic beads, glass beads or glass fibers between two liquid crystal display device substrates in order to maintain the thickness (cell gap) of a liquid crystal layer. I use it as a spacer across it. These spacers are arranged by scattering when assembling the liquid crystal display element.

In order to maintain a cell gap, Japanese Patent Application Laid-Open Nos. Sho 56-140324,
JP-A-4-93924 and JP-A-5-196946 include:
A liquid crystal display device using a structure in which colored layers forming a color filter are superposed as a spacer has been proposed.

[0004]

In a color liquid crystal display device using a plastic bead or the like as a spacer, the position of the spacer such as a plastic bead or the like is not fixed, and the display area on the liquid crystal display device substrate ( The spacer also exists in the light transmitting portion of the colored layer except the light shielding portion). There is a problem that the display quality of the liquid crystal display element is deteriorated due to scattering and transmission of light by the spacer.

A liquid crystal display element using a spacer such as a plastic bead dispersedly has the following other problems. That is, the spacers may not be uniformly dispersed in the liquid crystal display element, and the spacers may be partially accumulated. When such a phenomenon occurs, the display quality of the portion where the spacers are gathered is degraded, and there is also a problem in maintaining the cell gap accurately.

[0006] In a liquid crystal display device actually obtained by the above-mentioned disclosed technology using a structure in which colored layers forming a color filter are superposed as a spacer, the liquid crystal display device receives external force or impact. Display failure may occur. In particular, when a local force is applied, display unevenness is recognized and the display quality may be degraded. In addition, a problem may arise when the height of the formed spacers varies. When assembling a cell (panel), two liquid crystal display element substrates are attached by applying a certain amount of force. However, when the force pressing the substrate is removed, the spacer may return to its original height and the height of the spacer may become uneven. For this reason, the number of spacers that work effectively is reduced, the function of maintaining the cell gap is reduced, and the possibility of display unevenness is increased.

An object of the present invention is to realize a sufficient cell gap, maintain a uniform cell gap in a screen, eliminate display unevenness, and improve display quality when an external force or impact is applied. An object of the present invention is to provide a substrate for a liquid crystal display element which is less likely to be reduced than that of the above, and a color liquid crystal display element including the same.

[0008]

As a result of intensive studies on means for solving the above-mentioned problems, the present inventors have set the elastic recovery rate of the spacer within a specific range of compressive stress to a specific range. As a result, the present inventors have found that the above objects can be achieved, and have completed the present invention.

That is, the present invention has a spacer fixed to a non-display area on a substrate for a liquid crystal display element, and has an elastic recovery ratio with respect to a compressive stress of 0.4 to 0.6 GPa of the spacer. The present invention provides a liquid crystal display device substrate having a ratio of 20% to 80%. Further, the present invention includes a spacer including an acrylic resin fixed to a non-display region on a liquid crystal display element substrate, and the spacer recovers elasticity with respect to a compressive stress of 0.4 to 0.6 GPa. Provided is a substrate for a liquid crystal display device having a ratio of 0.01 to 80%. Furthermore, the present invention is characterized in that in a color liquid crystal display element in which a liquid crystal layer is sandwiched between two liquid crystal display element substrates, at least one of the liquid crystal display element substrates is the liquid crystal display element substrate of the present invention. To provide a color liquid crystal display device.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by taking as an example a case where a substrate for a liquid crystal display element is a color filter containing a colorant.

As the color filter, a filter in which a black matrix is provided on a transparent substrate and a plurality of coloring layers of three primary colors are further arranged thereon is preferable. Further, as the black matrix, a resin black matrix composed of a resin and a light shielding agent is preferable. The color filter is composed of a large number of picture elements, with pixels covered by each of the three primary color layers as one picture element. Here, the black matrix indicates a light-shielding region arranged between the pixels, and is provided to improve the display contrast of the liquid crystal display device.

The transparent substrate used for the color filter is not particularly limited, and inorganic glass such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass whose surface is coated with silica,
Organic plastic films or sheets are preferably used.

A black matrix is provided on the transparent substrate. The black matrix may be formed of a metal such as chromium or an oxide thereof, but it is preferable to form a resin black matrix composed of a resin and a light-shielding agent in terms of manufacturing costs and waste disposal costs. In this case, the resin used for the black matrix is not particularly limited, but is a photosensitive or non-photosensitive material such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, and a polyolefin resin. Is preferably used. The resin for the black matrix is preferably a resin having higher heat resistance than the resin used for the pixels and the protective film, and a polyimide resin is preferably a resin having resistance to the organic solvent used in the process after the formation of the black matrix. Resins are particularly preferably used. In addition, as a preferable polyimide resin, a resin suitable for forming a spacer described later can be mentioned.

Examples of the light shielding agent for the black matrix include metal oxide powders such as carbon black, titanium oxide and iron tetroxide, metal sulfide powders, metal powders, and mixtures of pigments such as red, blue and green. Can be used. Among them, carbon black is particularly preferable because of its excellent light shielding properties. Since carbon black having a good dispersion and a small particle size mainly exhibits a brownish color tone, it is preferable to mix a pigment of a complementary color to carbon black to obtain an achromatic color.

When the resin for the black matrix is polyimide, the black paste solvent is usually N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Amide polar solvents such as N, N-dimethylformamide,
A lactone polar solvent such as γ-butyrolactone is preferably used.

As a method of dispersing a light-shielding agent such as a pigment of a complementary color to carbon black or carbon black, for example, after mixing a light-shielding agent or a dispersant in a polyimide precursor solution, a three-roll Sand grinder,
There is a method of dispersing in a dispersing machine such as a ball mill, but the method is not particularly limited. In addition, various additives may be added for improving the dispersibility of carbon black, or for improving applicability and leveling property.

As a method for producing a resin black matrix, a black paste is applied on a transparent substrate, dried,
Perform patterning. As a method for applying the black paste, a dip method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, and the like are suitably used, and thereafter, heat drying (semi-curing) is performed using an oven or a hot plate. . The semi-curing conditions vary depending on the resin, solvent and paste coating material used, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.

In the case where the resin is a non-photosensitive resin, the black paste film thus obtained is formed after forming a positive type photoresist film on the non-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 the film is dried by heating (this cure). These curing conditions are slightly different depending on the coating amount when a polyimide resin is obtained from the precursor, but it is generally heated at 200 to 300 ° C. for 1 to 60 minutes. Through the above process, a black matrix is formed on the transparent substrate.

The resin black matrix may be formed by a so-called transfer method. That is, a transfer film in which a black layer with photosensitivity is formed on a substrate in advance is prepared, and the transfer film is overlaid on a substrate (applying heat and pressure as necessary), exposed and developed, and then In this method, a base material is peeled off to form a resin black matrix on a substrate.

The thickness of the resin black matrix is preferably 0.5 to 2.0 μm, more preferably 0.8 to 2.0 μm.
1.5 μm. If the thickness is smaller than 0.5 μm, it is difficult to secure a sufficient cell gap, and
It is not preferable because the light-shielding property becomes insufficient. on the other hand,
When the film thickness is greater than 2.0 μm, the light-shielding property can be ensured, but the flatness of the color filter is easily sacrificed and a step is likely to occur.

The substrate for a liquid crystal display element of the present invention has a spacer fixed in a non-display area. When the liquid crystal display element substrate is a color filter as described above, it is preferable to form a spacer on the black matrix which is a non-display area.

In the substrate for a liquid crystal display element of the present invention, the spacer has an elastic recovery ratio of from 20 to 80%, preferably from 25 to 75, for a compressive stress of 0.4 to 0.6 GPa.
%, More preferably 30 to 70%. When the elastic recovery rate is less than 20%, a liquid crystal display element is manufactured using a liquid crystal display element substrate, and when a force or impact is applied to the display surface from the outside, display unevenness occurs and the display quality deteriorates. On the other hand, when the elastic recovery ratio exceeds 80%, display unevenness tends to occur on the display surface of the liquid crystal display element. When the spacer contains an acrylic resin, the elastic recovery is 0.01 to 80%, preferably 0.01 to 70%, more preferably 0.1 to 60%, and 1 to 50%.
% Is more preferred. In the case of an acrylic resin, if the elastic recovery is less than 0.01%, a liquid crystal display element is manufactured using a liquid crystal display element substrate, and display unevenness is caused when an external force or impact is applied to the display surface. This causes the display quality to deteriorate. On the other hand, when the elastic recovery ratio exceeds 80%, display unevenness tends to occur on the display surface of the liquid crystal display element. The elastic recovery ratio of the spacer is 20% to 80% or 0.01% at one point in the range of 0.4 to 0.6 GPa of compressive stress.
Those falling within the range of ８０80% are included in the scope of the present invention.

The liquid crystal display device is manufactured by bonding two substrates for a liquid crystal display device. At this time, the substrate has 10
A compressive stress of about 0 to 1000 Pa is applied. On average, the spacer formed to maintain the gap between the two substrates is subjected to a compressive stress of a value obtained by dividing the compressive stress applied to the substrate by the total cross-sectional area of the spacer.
Therefore, the compressive stress applied to one spacer differs depending on the density of the formed spacer and the cross-sectional area of one spacer. Generally, the compressive stress applied to one spacer is about 0.1 to 1 GPa, and focusing on the compressive stress within that range, particularly 0.4 to 0.6 GPa,
The elastic recovery was measured.

The restoration ratio of the spacer to the compressive stress in the present invention can be measured as follows. That is, using a micro compression tester or the like, a load is applied to one spacer while the indentation load is increased at a constant speed. When the indentation load becomes F _2, this time continue to unload until the final indentation load becomes F ₁ while decreasing the indentation load at a constant speed. In this loading-unloading process,
Measure the indentation displacement. FIG. 2 is a diagram in which the indentation load is plotted on the horizontal axis and the indentation displacement is plotted on the vertical axis. Note that the indentation displacement does not necessarily need to be continuously measured, and at least the displacement L at the time of the final indentation load F ₁ in the loading step is determined.
_a, indentation depth o'clock indentation load F ₂ when reversing the unloading from the load L _C, may be measured displacements o'clock final indentation load F ₁ in the unloading step L _b (see FIG. 2). The elastic recovery rate is obtained by the following equation [I].

[0025]

(Equation 1)

The indentation load F ₂ is set so that the compressive stress when F ₂ is applied is 0.4 to 0.6 GPa. The compressive stress is calculated by changing F ₂ to the area S of the flat portion on the top surface of the spacer.
It is determined by dividing the (F area at ₂ load). S
Can be measured by using a microscope or the like.
Further, the final indentation load F ₁ is such that the compressive stress under the load of F ₁ is 0.
０．０0.06 GPa.

The shape of the spacer, that is, the cross-sectional shape when the spacer is cut along a plane parallel to the substrate is not particularly limited, but may be a circle, an ellipse, a polygon having rounded corners, a cross, or the like.
A T or L shape is preferred.

The height of the spacer is preferably from 1 to 9 μm, more preferably from 2 to 8 μm. When the height of the spacer is lower than 1 μm, it is difficult to secure a sufficient cell gap. On the other hand, when the thickness exceeds 9 μm, the cell gap of the liquid crystal display element becomes too large, and the voltage required for driving becomes high, which is not preferable. Here,
Focusing on one spacer, the height of the spacer refers to the flat portion of the display portion (in the case of a color filter, the colored layer, TF
Means the distance between the transparent electrode in the case of a T substrate) and the uppermost surface of the spacer. If there is unevenness in the height of the display flat portion on the substrate, it means the largest of the distances between the uppermost surface of the spacer and each display flat portion.

When two liquid crystal display element substrates are bonded to each other to form a liquid crystal display element, the area where the spacer contacts the opposing substrate is 10 to 1000 μm.
m ² is preferred. If this area is less than 10 μm ² ,
It is difficult to form and laminate a precise pattern, 1000 .mu.m ²
Exceeding the range is not preferable because it is difficult to completely dispose it on the non-display area, though it depends on the shape of the spacer.

As a material constituting the spacer, a material which can obtain the above-mentioned specific elastic recovery rate specified in the present invention is selected and used. As such a material, a photosensitive or non-photosensitive material such as a polyimide resin, an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, and a polyolefin resin is preferably used. It goes without saying that among these materials, those satisfying the above-mentioned elastic recovery rate are selected and used. As described below, when a spacer is formed with a colored layer, a colored material obtained by dispersing or dissolving a colorant in these resins is used as the spacer. Examples of the photosensitive resin include photodecomposable resins, photocrosslinkable resins, and photopolymerizable resins.Especially, monomers having an ethylenically unsaturated bond, an oligomer or a polymer, and an initiator that generates radicals by ultraviolet rays are used. A photosensitive composition containing, for example, a photosensitive polyamic acid composition is suitably used. As the non-photosensitive resin, those which can be developed with the above-mentioned various polymers are preferably used. However, heat-resistant resins capable of withstanding such heat in the process of forming a transparent conductive film and the process of manufacturing a liquid crystal display device are preferably used. Is preferable, and a resin having resistance to an organic solvent used in a manufacturing process of a liquid crystal display device is preferable.
Needless to say, a resin that easily obtains the resin having the above-mentioned elastic recovery rate is preferable, and a polyimide resin is particularly preferable.

Here, the polyimide resin is not particularly limited, but is usually a polyimide precursor (n = 1) having a structural unit represented by the following general formula [I] as a main component.
~ 2) obtained by imidizing by heating or using a suitable catalyst are suitably used.

[0032]

Embedded image

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

In the general formula [I], R ¹ is a trivalent or tetravalent organic group having at least two or more carbon atoms.
From the viewpoint of heat resistance, R ¹ is preferably a trivalent or tetravalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Examples of R ¹ include phenyl, biphenyl, terphenyl, naphthalene, perylene, diphenylether, diphenylsulfone, diphenylpropane, benzophenone, biphenyltrifluoropropane, cyclobutyl, cyclopentyl, and the like. But not limited to these.

R ² is a divalent organic group having at least two or more carbon atoms. From the viewpoint of heat resistance, R ² contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring, and A divalent group having 6 to 30 carbon atoms is preferable. Examples of R ² include a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenylether group, a diphenylsulfone group, a diphenylpropane group, a benzophenone group, a biphenyltrifluoropropane group, a diphenylmethane group, and a cyclohexylmethane group. But not limited thereto. The polymer having the structural unit [I] as a main component may be a copolymer in which R ¹ and R ² are each composed of one or more of them. . Further, in order to improve the adhesiveness to the substrate, it is preferable to copolymerize bis (3-aminopropyl) tetramethyldisiloxane having a siloxane structure as the diamine component as long as the heat resistance is not reduced.

Specific examples of the polymer having the structural unit [I] as a main component include pyromellitic dianhydride, 3,3 ′, 4,4′-
Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-
Selected from the group consisting of biphenyltrifluoropropanetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, etc. One or more carboxylic dianhydrides, paraphenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4 , 4'-Diaminodiphenylsulfone, 4,4'-Diaminodicyclohexylmethane, 4,4'-
Examples include, but are not limited to, polyimide precursors synthesized from one or more diamines selected from the group such as diaminodiphenylmethane. These polyimide precursors are synthesized by a known method, that is, by selectively combining tetracarboxylic dianhydride and diamine and reacting them in a solvent.

Also, a spacer containing an acrylic resin is preferable. As the acrylic resin used at this time, acrylic acid, methacrylic acid, methyl acrylate,
Alkyl acrylates or alkyl methacrylates such as methyl methacrylate, cyclic acrylates or methacrylates, hydroxyethyl acrylates or methacrylates, among which about 3 to 5 types of monomers are used, and a resin synthesized to a molecular weight of about 5,000 to 100,000 is preferably used. . When the spacer contains an acrylic resin, the content of the acrylic resin in the components constituting the spacer is preferably 50% by weight or more, and more preferably 60% by weight or more.

The material constituting the spacer may be either photosensitive or non-photosensitive, but a photosensitive material is preferably used from the viewpoint of ease of fine processing. In the case of a photosensitive resin, a composition comprising a resin, a photopolymerizable monomer, and a photopolymerization initiator is preferably used.

When the resin is an acrylic resin, the photopolymerizable monomer includes bifunctional, trifunctional, and polyfunctional monomers. Examples of the bifunctional monomer include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, Neopentyl glycol diacrylate, triethylene glycol acrylate and the like, as trifunctional monomer, trimethylolpropane triacrylate,
Pentaerythritol triacrylate, tris (2-
(Hydroxyethyl) isocyanate, and polyfunctional monomers such as ditrimethylolpropanetetraacrylate, dipentaerythritol penta, and hexaacrylate.

As the photopolymerization initiator, benzophenone, thioxanthone, imidazole, triazine and the like can be used alone or in combination.

The spacer is made of the above-mentioned material. The colored layer is made of such a material, and the colored layer remains on the black matrix when the colored layer is patterned by photolithography. The spacer may be formed on the black matrix by patterning as described above. In the case of a color filter, the coloring layer includes three layers of red (R), green (G) and blue (B), and each pixel has one coloring layer of any of these three colors. Provided. The spacer can be composed of one, two or three of these colored layers. Coloring layer 1
When the spacer is composed of layers, the spacer consists of a single color of the resin containing the colorant, and when the spacer is composed of two or three layers, the spacer is the colorant. ). In order to secure a sufficient cell gap, it is usually preferable to form a spacer with three colored layers.

The coloring layer constituting the color filter contains at least three primary colors. That is, when performing color display by the additive color method, three primary colors of red (R), green (G), and blue (B) are selected. When performing color display by the subtractive color method, cyan (C) and magenta are used. (M) and three primary colors of yellow (Y) are selected. Generally, a picture element for color display can be formed by using an element including these three primary colors as one unit. For the coloring layer, a resin colored with a coloring agent is used.

As the coloring agent used in the coloring layer, organic pigments, inorganic pigments, dyes and the like can be suitably used. Further, various additives such as an ultraviolet absorber, a dispersing agent and a leveling agent are added. You may. As the organic pigment, phthalocyanine-based, aziraki-based, condensed azo-based, quinacridone-based, anthraquinone-based, perylene-based, and perinone-based pigments are preferably used. As the pigment, Co (red)
lor Index No. 9, 97, 122, 123, 149, 1
68, 177, 180, 192, 215, etc., Color Index No. 7, 36 etc. as green (G), Co as blue (B)
lor Index Nos. 15, 22, 60, 64 and the like are generally used. A wide range of dispersants such as surfactants, pigment intermediates, dye intermediates, and sorbers are used.

As a method for forming a colored layer, patterning is performed after coating and drying on a substrate on which a resin black matrix is formed. As a method of obtaining a colored paste by dispersing or dissolving the colorant, after mixing the resin and the colorant in a solvent, three-roll, sand grinder, there is a method of dispersing in a dispersing machine such as a ball mill, The method is not particularly limited.

As a method of applying the colored paste, a dipping method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, or the like is preferably used, as in the case of the black paste. Heat drying (semi-cure) is performed using a plate. The semi-curing conditions vary depending on the resin used, the solvent, and the amount of the paste applied, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.

In the case where the resin is a non-photosensitive resin, the colored paste film thus obtained is formed after forming a positive photoresist film thereon, 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 type photoresist or the oxygen blocking film is removed and dried by heating (this cure). The curing conditions vary depending on the resin, but when a polyimide resin is obtained from the precursor, it is generally heated at 200 to 300 ° C. for 1 to 60 minutes. In the case of acrylic resin, usually 15
Generally, heating is performed at 0 to 300 ° C. for 1 to 60 minutes.
Through the above process, a patterned colored layer is formed on the substrate on which the black matrix is formed. Further, the colored layer may be formed by a so-called transfer method.

After the first color layer is formed over the entire surface of the substrate on which the black matrix is formed as described above, unnecessary portions are removed by photolithography to obtain a desired pattern of the first color layer. To form
In the case where the spacer is formed by lamination of colored layers, the colored layer is left in a portion that covers at least the opening of the black matrix and a portion in which a spacer is formed by laminating the colored layer. The same operation is repeated for the second color and the third color, and a colored layer is formed such that one colored layer remains on the opening of the black matrix, and preferably three colored layers remain as a spacer. I do. The colored layer on the opening and the colored layer forming the spacer may be continuous or separated. However, indium tin oxide (ITO) formed as a transparent electrode on the color filter
When disconnecting the film between the colored layer on the opening and the spacer to prevent conduction between the color filter side and the opposing substrate,
It is preferable that the coloring layer on the opening and the coloring layer forming the spacer be separated and fractionated.

The above description has been made mainly on the case where the liquid crystal display element substrate is a color filter. However, the present invention is not limited to this, and may be a monochrome filter or a TFT substrate. Note that a substrate having a plurality of transistors may be used. In the case of a TFT substrate, the spacer is formed on a non-display area between the transparent electrodes. The above description of the constituent material, shape, height, cross-sectional area, and the like of the spacer also applies to a TFT substrate as it is.

Next, a color liquid crystal display device manufactured using the above color filter and TFT substrate will be described. FIG. 1 is a schematic sectional view of a preferred embodiment of the color liquid crystal display device. In FIG. 1, 13 is a transparent substrate, 12 is a black matrix, 9 is a colored layer such as (B), 10 is a colored layer such as (R), 11 is a colored layer such as (G), 8 is a transparent electrode, and 6 is an alignment film. It is. 14, 1
5 and 16 are spacers formed by laminating the respective colored layers. On the other hand, 1 is a transparent substrate of a transparent electrode substrate facing the color filter, 2 is a gate electrode, 3 is an insulating film, 4 is a pixel electrode, 5 is a TFT, and 6 is an alignment film as described above. Reference numeral 7 denotes a liquid crystal sandwiched between the color filter and the transparent electrode substrate. As shown in FIG. 1, the liquid crystal display device is manufactured with the above-mentioned color filter and the transparent electrode substrate facing each other. The color filter may be provided with a transparent protective film on the colored layer if necessary,
The configuration becomes complicated, and the manufacturing cost increases. Further, the spacer height is reduced by the leveling property of the transparent protective film. Further, a transparent electrode such as an ITO film is formed on the color filter. As the transparent electrode substrate facing the color filter, a transparent electrode such as an ITO film is provided in a pattern on the transparent substrate. On the transparent electrode substrate,
In addition to transparent electrodes, TFT elements and thin-film diodes (TF
D) An element, a scanning line, a signal line, and the like are provided, and a TFT liquid crystal display element and a TFD liquid crystal display element can be manufactured. A liquid crystal alignment film is provided on the color filter having a transparent electrode and the transparent electrode substrate, and is subjected to an alignment process such as rubbing. After the alignment treatment, the color filter and the transparent electrode substrate are attached to each other using a sealant, and after the liquid crystal is injected from an inlet provided in the seal portion, the inlet is sealed. The module is completed by mounting an IC driver and the like after attaching the polarizing plate to the outside of the substrate. A liquid crystal display element without a transparent electrode on the color filter side, for example, in-plane switching (IPS)
In the case of the method called, a configuration corresponding to this is also provided.

The liquid crystal display device substrate of the present invention and the color liquid crystal display device using the same are used for display screens of personal computers, word processors, engineering workstations, navigation systems, liquid crystal televisions, videos, etc. And the like.

[0051]

The present invention will be described more specifically below with reference to examples. However, the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “parts” means “parts by weight” unless otherwise specified.

Example 1 (1) Preparation of resin black matrix and seal portion pattern 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'
-Diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane with N-methyl-
The reaction was performed in a 2-pyrrolidone solvent to obtain a polyimide precursor (polyamic acid) solution having a polymer concentration of 20% by weight.

A carbon black mill base having the following composition was dispersed at 7000 rpm for 30 minutes using a homogenizer, and the glass beads were filtered to prepare a black paste.

Carbon black mill base Carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) 4.6 parts Polyimide precursor solution 24.0 parts N-methylpyrrolidone 61.4 parts Glass beads 90.0 parts

A black paste was applied to a 300 × 350 mm non-alkali glass substrate (OA-2, manufactured by NEC Corporation) using a spinner, and the plate was placed in an oven.
Semi-cure at 35 ° C. for 20 minutes. Subsequently, a positive resist (Shipley "Microposit" RC100 30 cp) was applied with a spinner and dried at 90 ° C. for 10 minutes. The resist film thickness was 1.5 μm. Exposure machine PLA-5 manufactured by Canon Inc.
Using 01F, exposure was performed through a photomask.

Next, an aqueous solution at 23 ° C. containing 2% by weight of tetramethylammonium hydroxide was used as a developing solution, and the substrate was dipped in the developing solution. Then, the development of the positive resist and the etching of the polyimide precursor were simultaneously performed.
The development time was 60 seconds. After that, the positive resist was peeled off with methylcellosolve acetate, and further, 300
The mixture was cured at a temperature of 30 ° C. for 30 minutes to be converted into polyimide, thereby obtaining a resin black matrix substrate. The thickness of the resin black matrix was 1.0 μm.

(2) Preparation of Colored Layer and Spacer Next, Color Index No. 653 was used as a red, green and blue pigment, respectively.
00 Dianthraquinone pigment represented by Pigment Red 177, Color Index No. 74265 Phthalocyanine green pigment represented by Pigment Green 36, Color Index No. 741
A phthalocyanine blue pigment represented by 60 Pigment Blue 15-4 was prepared. The pigments were mixed and dispersed in a polyimide precursor solution at a weight ratio (polyimide precursor / pigment) of 8: 2 to obtain three kinds of colored pastes of red, green and blue.

First, a blue paste was applied on a resin black matrix substrate and dried with hot air at 80 ° C. for 10 minutes.
Semi-cure at 20 ° C. for 20 minutes. Thereafter, a positive resist (Shipley "Microposit" RC100 30 cp) was applied by a spinner and dried at 80 ° C. for 20 minutes. Exposure was performed using a mask, the substrate was dipped in an alkali developing solution (Shipley "Microposit" 351), and simultaneously developing the positive resist and etching the polyimide precursor were performed while simultaneously swinging the substrate. Thereafter, the positive resist was stripped with methyl cellosolve acetate, and cured at 300 ° C. for 30 minutes. The thickness of the colored pixel portion was 2.0 μm. By this patterning, the first step of the spacer was formed on the resin black matrix together with the formation of the blue pixel.

After washing with water, the second stage of the spacer was similarly formed on the resin black matrix together with the formation of the red pixel. The thickness of the red pixel portion was 1.8 μm.

After further washing with water, similarly to the formation of green pixels, a spacer 3
Steps were formed to produce a color filter. The thickness of the green pixel portion was 1.9 μm.

The area of the bottom of the spacer provided on the resin black matrix by lamination of the colored layers was about 500 μm ² per piece. Spacer height is about 4μm
Met. The spacer was provided in the screen at a rate of one for every three pixels. Further, the shape of the spacer was almost circular. In addition, a spacer was also provided on a part of the frame formed of a resin black matrix around the screen at the same density as in the screen.

On a non-alkali glass substrate having this light-shielding layer, a red pixel, a green pixel, and a blue pixel, and a spacer on a resin black matrix of a display screen portion, a frame, and a sealing portion around the frame, a sputtering process is performed. An ITO film was formed by the method, and a color filter used as a substrate for a liquid crystal display device was obtained. The thickness of the ITO film was 150 nm, and the surface resistance was 20 Ω / □.

(3) Measurement of elastic recovery of spacer The elastic recovery of one spacer (4 μm in height) was measured using a micro compression tester (MCTE-500, Shimadzu Corporation). The test conditions, the load (unloading) rate 2.582mN / s, the load → unloading when reversing indentation load F ₂
The 60 mN, the final indentation load F ₁ at the time of unloading was 5 mN. When the area of the uppermost flat portion of the spacer after a load of 60 mN was measured using an optical microscope, it was 128 μm.
^{Was 2} . Therefore, the compressive stress at this time is 0.5 GPa
It is. Indentation depth L in the final indentation load F ₁ at the time of load
_a is 0.2μm, load → displacement L _c at the time of unloading reversal 1.1
2 [mu] m, the displacement L _b at the final indentation load 5mN during unloading was 0.62 .mu.m. When these values were substituted into the above formula [I] and calculated, the elastic recovery rate was 54%.

(4) Production and evaluation of color liquid crystal display device ITO of color filter provided with this spacer
A polyimide-based alignment film was provided on the film, and a rubbing treatment was performed. Similarly, a facing liquid crystal display element substrate was also provided with a polyimide-based alignment film and subjected to a rubbing treatment. After bonding these two substrates together using an epoxy adhesive as a sealant, liquid crystal was injected from an injection port provided in the seal portion. After injecting the liquid crystal, seal the injection port,
Further, a polarizing plate was attached to the outside of the substrate to produce a liquid crystal display device.

The display characteristics of this liquid crystal display element were uniformly good over the entire display surface. I tried to press a part of the display surface with my finger, but there was no change in display quality after and before pressing.

Comparative Example 1 (1) Preparation of Resin Black Matrix and Seal Part Pattern A resin black matrix and a seal part pattern were prepared in the same manner as in Example by using a solution of carbon black and an epoxy silicone resin containing a carboxyl group. Was done.

(2) Preparation of Colored Layer and Spacer Using the same method as in the example, the red, green and blue pigments were added to the epoxy / silicone resin containing a carboxyl group in a weight ratio of (resin / pigment). Red, green, and blue pixels are formed using three types of colored pastes of red, green, and blue obtained by mixing and dispersing at a ratio of 1/9, and at the same time, a display screen portion and a frame, A spacer was formed on the resin black matrix in the seal around the picture frame.

An ITO film was formed on the substrate having the spacer by a sputtering method to obtain a color filter as one of the substrates for a liquid crystal display device.

(3) Measurement of elastic recovery rate The elastic recovery rate of one of the formed spacers (height: 4 μm) was measured in the same manner as in the example. The restoration rate was 15%.

(4) Production and Evaluation of Color Liquid Crystal Display Element A liquid crystal display element was produced in the same manner as in the example, using the liquid crystal display element substrate provided with the spacers. When a part of the display surface was strongly pressed with a finger, display unevenness was partially generated, and the unevenness did not disappear shortly after the finger pressing was stopped, and the display quality was significantly reduced.

Comparative Example 2 (1) Preparation of Metal Black Matrix and Seal Pattern A light-shielding film made of chromium and its oxide was formed on a transparent substrate by vacuum evaporation. A photoresist was applied thereto and dried by heating to form a photoresist film. This was exposed through a photomask using an ultraviolet exposure machine. After the exposure, the photoresist was immersed in an alkaline developer to develop the photoresist. Thereafter, the light-shielding film was etched with an acid developer, and after the etching, the unnecessary photoresist layer was peeled off to form a black matrix.

(2) Production of Colored Layer A red pixel, a green pixel, and a blue pixel were formed by using the same method as that of the embodiment. At this time, unlike the embodiment, no spacer was formed on the black matrix of the display screen portion, the frame, and the seal portion around the frame.

(3) Production of spacer A spacer composed of a silicon oxide film was formed on a black matrix by mask sputtering.

An ITO layer was formed on the substrate having the spacer by a sputtering method to obtain a color filter used as a substrate for a liquid crystal display device.

(4) Measurement of elastic recovery rate The elastic recovery rate of one of the formed spacers (height: 4 μm) was measured in the same manner as in the example. The restoration rate was 90%.

(5) Production and evaluation of color liquid crystal display device When a liquid crystal display device was produced in the same manner as in the example using the liquid crystal display device substrate provided with the spacers, display unevenness occurred partially, and Degradation was seen.

Example 2 (1) Production of Resin Black Matrix and Seal Part Pattern In the same manner as in Example 1, a resin black matrix and a seal part pattern were prepared by using a paste obtained by dispersing and mixing a carbon black matrix in a polyimide precursor solution. Was prepared.

(2) Production of Colored Layer and Spacer Using the same method as in Example 1, the polyimide precursor solution and the red, green, and blue pigments were each mixed at a weight ratio (polyimide precursor / pigment) of 9 / It was obtained by mixing and dispersing at a ratio of 1.
Red, green, and blue pixels are formed using three types of colored pastes of red, green, and blue, and at the same time, a spacer is formed on the resin black matrix of the display screen, the frame, and the seal around the frame. The formation was performed.

An ITO layer was formed on the substrate having the spacer by a sputtering method to obtain a color filter used as a substrate for a liquid crystal display device.

(3) Elastic recovery ratio The elastic recovery ratio of one of the formed spacers (height: 6 μm) was measured in the same manner as in Example 1.
Met.

(4) Production and Evaluation of Color Liquid Crystal Display Element A liquid crystal display element was produced in the same manner as in Example 1. The display quality of this liquid crystal display element was good. When a part of the display surface was strongly pressed with a finger, there was no change in display quality after and before pressing.

Example 3 (1) Production of Resin Black Matrix and Seal Part Pattern In the same manner as in Example 1, a resin black matrix and a seal part pattern were prepared by using a paste obtained by dispersing and mixing a carbon black matrix in a polyimide precursor solution. Was prepared.

(2) Preparation of Colored Layer and Spacer Using the same method as in Example 1, the polyimide precursor solution and the red, green, and blue pigments (polyimide precursor / pigment) at a weight ratio of 3 / Obtained by mixing and dispersing at a ratio of 7.
Red, green, and blue pixels are formed using three types of colored pastes of red, green, and blue, and at the same time, a spacer is formed on the resin black matrix of the display screen, the frame, and the seal around the frame. The formation was performed.

An ITO layer was formed on the substrate having the spacer by a sputtering method to obtain a color filter used as a substrate for a liquid crystal display device.

(3) Measurement of elastic recovery ratio The elastic recovery ratio of one of the formed spacers (5 μm in height) was measured in the same manner as in Example 1, and was found to be 73%.
Met.

(4) Production and Evaluation of Color Liquid Crystal Display Element A liquid crystal display element was produced in the same manner as in Example 1. The display quality of this liquid crystal display element was good. When a part of the display surface was strongly pressed with a finger, a steady decrease in display quality was not observed after and before pressing.

Example 4 (1) Production of Resin Black Matrix and Seal Part Pattern A resin black matrix and a seal part pattern were produced in the same manner as in Example 1.

(2) Preparation of Colored Layer and Spacer An acrylic resin (20 parts of methacrylic acid, 10 parts of methyl methacrylate, 55 parts of butyl methacrylate, and 15 parts of hydroxyethyl methacrylate was added to an ethyl cellosolve 300).
g), and 0.75 parts of azobisisobutylnitrile was added thereto under a nitrogen atmosphere, and an acrylic resin obtained by a reaction at 70 ° C. for 5 hours was diluted with ethyl cellosolve to a resin concentration of 10%.

The pigment 5.7 was added to 94 g of the diluted resin.
g, and 0.3 g of a dispersant, and kneaded well with a three-roll mill to produce a red, green, and blue colored paste. Color index No.65300 Pigment Red 1 for red, green and blue pigments respectively
Dianthraquinone pigment represented by 77, Color Index N
o.Phthalocyanine green pigment represented by 74265 Pigment Green 36, Color Index No. 74160 Pigment Blue
A phthalocyanine blue pigment represented by 15-4 was used.

First, a blue paste was applied on a resin black matrix substrate and dried. After drying with hot air at 80 ° C. for 10 minutes, a 5% solution of polyvinyl alcohol was applied to form an oxygen barrier film. After drying at 80 ° C. for 10 minutes, exposure was performed using a mask, the substrate was dipped in a developing solution (aqueous sodium carbonate solution), and etching was performed while simultaneously rocking the substrate. Thereafter, brush cleaning was performed with pure water. After washing and drying,
Cure at 230 ° C. for 60 minutes. The thickness of the colored pixel portion was 2.2 μm. By this patterning, the first step of the spacer was formed on the resin black matrix together with the formation of the blue pixel.

After washing with water, the second step of the spacer was formed on the resin black matrix together with the formation of the red pixel in the same manner. The thickness of the red pixel portion was 1.9 μm.

Further, after washing with water, the third step of the spacer was formed on the resin black matrix together with the formation of the green pixel in the same manner to produce a color filter. The thickness of the green pixel portion was 2.0 μm.

The height of the spacer provided on the resin black matrix by laminating the colored layers was about 4 μm. The spacers were provided in the screen at a ratio of two for three pixels. The shape of the spacer was substantially circular. In addition, spacers are provided on a part of the frame formed of a resin black matrix around the screen by color overlapping at the same density as in the screen.

On a non-alkali glass substrate having this light-shielding layer, a red pixel, a green pixel, and a blue pixel, and a spacer on a resin black matrix of a display screen portion, a frame, and a sealing portion around the frame, a sputtering method is used. Thus, an ITO film was formed to obtain a color filter used as a substrate for a liquid crystal display device. The thickness of the ITO film was 150 nm, and the surface resistance was 15 Ω / □.

(3) Measurement of the elastic recovery rate of the spacer The elastic recovery rate of one formed spacer (3.5 μm in height) was measured in the same manner as in Example 1, and the compressive stress was 0.5 GPa. The elastic recovery was 26%.

(4) Production and evaluation of color liquid crystal display element A liquid crystal display element was produced in the same manner as in Example 1 using the liquid crystal display element substrate provided with the spacers. The display characteristics of this liquid crystal display element were uniformly good. I tried to press a part of the display surface with my finger, but there was no change in display quality after and before pressing.

Comparative Example 3 (1) Preparation of Resin Black Matrix and Seal Pattern A black pigment containing carbon black was added to a solution of an epoxy silicone resin containing a carboxyl group (resin / pigment).
Using a black paste mixed and dispersed at a weight ratio of 25/75, a resin black matrix and a seal portion pattern were produced in the same manner as in Example 1.

(2) Preparation of Colored Layer and Spacer Using the same method as in Example 4, a red pigment was added to the epoxy / silicone resin containing a carboxyl group (resin / pigment).
The mixture was mixed and dispersed at a weight ratio of 8/92 to obtain a red colored paste. Similarly, a green pigment (resin / pigment) weight ratio of 1
0/90 ratio, blue pigment (resin / pigment) weight ratio 5 /
The mixture was dispersed and mixed at a ratio of 95 to obtain green and blue colored pastes, respectively. Using these three types of colored pastes, a red pixel, a green pixel, and a blue pixel were formed, and at the same time, a spacer was formed on the resin black matrix of the display screen portion, the frame, and the seal portion around the frame.

On the substrate having the spacers, an ITO film was formed by a sputtering method to obtain a color filter which is one of the substrates for a liquid crystal display device.

(3) Measurement of Elastic Restoration Rate of Spacer The elastic restoring rate of one formed spacer (3.5 μm in height) was measured in the same manner as in Example 1, and the compression stress was 0.6 GPa. , Elastic recovery rate is 0.005
%Met.

(4) Production and evaluation of color liquid crystal display element A liquid crystal display element was produced in the same manner as in Example 1 using the liquid crystal display element substrate provided with the spacers. When the display was driven, large display unevenness occurred. When a part of the display surface was strongly pressed with a finger, the display unevenness was further deteriorated. The unevenness did not disappear even when the finger pressing was stopped, and the display quality was significantly reduced.

Comparative Example 4 (1) Production of Metal Black Matrix and Seal Pattern A light-shielding film made of chromium and its oxide was formed on a transparent substrate by vacuum evaporation. A photoresist was applied thereto and dried by heating to form a photoresist film. This was exposed through a photomask using an ultraviolet exposure machine. After the exposure, the photoresist was immersed in an alkaline developer to develop the photoresist. Thereafter, the light-shielding film was etched with an acid developer, and after the etching, the unnecessary photoresist layer was peeled off to form a black matrix.

(2) Production of Colored Layer Using the same method as in the fourth embodiment, a red pixel, a green pixel,
Blue pixels were formed. At this time, unlike the fourth embodiment, no spacer was formed on the black matrix of the display screen, the frame, and the seal around the frame.

(3) Production of Spacer A spacer composed of a silicon oxide film was formed on a black matrix by mask sputtering.

An ITO layer was formed on the substrate having the spacer by a sputtering method to obtain a color filter used as a substrate for a liquid crystal display device.

(4) Measurement of Elastic Restoration Ratio of Spacer The elastic restoration ratio of one formed spacer (3.5 μm in height) was measured in the same manner as in Example 1, and the compression stress was 0.5 GPa. The elastic recovery was 85%.

(5) Production and evaluation of color liquid crystal display element A liquid crystal display element was produced in the same manner as in Example 1 by using the liquid crystal display element substrate provided with the spacers. Display quality declined.

Example 5 (1) Production of Resin Black Matrix and Seal Part Pattern In the same manner as in Example 1, a resin black matrix and a seal part pattern were prepared by using a paste obtained by dispersing and mixing a carbon black matrix in a polyimide precursor solution. Was prepared.

(2) Preparation of Colored Layer and Spacer Using the same method as in Example 4, the diluted acrylic resin was
Each of red, green and blue pigments (diluent resin / pigment) weight ratio 95
3 of red, green, and blue obtained by mixing and dispersing at a ratio of / 5.
Red, green, and blue pixels were formed using various kinds of colored pastes, and at the same time, spacers were formed on the resin black matrix of the display screen, the frame, and the seal around the frame.

On the substrate having the spacers, an ITO layer was formed by a sputtering method to obtain a color filter used as a substrate for a liquid crystal display device.

(3) Measurement of Elastic Restoration Ratio of Spacer The elastic restoration ratio of one formed spacer (height: 6 μm) was measured in the same manner as in Example 1 to find that it was 0.5.
%Met.

(4) Production and Evaluation of Color Liquid Crystal Display Element A liquid crystal display element was produced in the same manner as in Example 1. The display quality of this liquid crystal display element was good. When a part of the display surface was strongly pressed with a finger, there was no change in display quality after and before pressing.

Example 6 (1) Production of Resin Black Matrix and Seal Part Pattern In the same manner as in Example 1, a resin black matrix and a seal part pattern were prepared by using a paste obtained by dispersing and mixing a carbon black matrix in a polyimide precursor solution. Was prepared.

(2) Preparation of Colored Layer and Spacer Using the same method as in Example 4, the diluted acrylic resin was
Red, green, and blue pigments (diluted resin / pigment) in a weight ratio of 3 /
Red, green, and blue pixels are formed by using three types of coloring pastes of red, green, and blue obtained by mixing and dispersing at a ratio of 7 and at the same time, around the display screen portion, the frame, and the frame. A spacer was formed on the resin black matrix of the seal part of the part.

On the substrate having the spacers, an ITO layer was formed by a sputtering method to obtain a color filter used as a substrate for a liquid crystal display device.

(3) Measurement of Elastic Restoration Ratio of Spacer The elastic restoration ratio of one formed spacer (3 μm in height) was measured in the same manner as in Example 1, and it was 57%.
Met.

(4) Production and Evaluation of Color Liquid Crystal Display Element A liquid crystal display element was produced in the same manner as in Example 1. The display quality of this liquid crystal display element was good. When a part of the display surface was strongly pressed with a finger, a steady decrease in display quality was not observed after and before pressing.

[0118]

According to the liquid crystal display device substrate of the present invention, the elastic recovery rate of the spacer in a specific compressive stress range is within a specific range. Therefore, when a liquid crystal display device is manufactured using this substrate, This has the effect that display unevenness is unlikely to occur, and that display characteristics are unlikely to be degraded even when an external force or impact is applied.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a color liquid crystal display device using a color filter of the present invention.

FIG. 2 is a diagram illustrating an example of a relationship between a pushing load and a pushing displacement in a loading step and an unloading step when measuring an elastic recovery rate of a spacer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Gate electrode 3 Insulating film 4 Pixel electrode 5 TFT 6 Alignment film 7 Liquid crystal 8 Transparent electrode 9 Colored layer 10 Colored layer 11 Colored layer 12 Black matrix 13 Transparent substrate 14 Spacer 15 Spacer 16 Spacer

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Tetsuya Goto 1-1-1 Sonoyama, Otsu-shi, Shiga Pref.

Claims (14)

[Claims] 1. A spacer fixed to a non-display area on a liquid crystal display element substrate, wherein the spacer has a width of 0.4 to
Elastic recovery rate for compressive stress of 0.6 GPa is 20 to 8
0% liquid crystal display element substrate. 2. The liquid crystal display device substrate according to claim 1, wherein the elastic recovery ratio is 25 to 75%. 3. The substrate for a liquid crystal display device according to claim 2, wherein said elastic recovery rate is 30 to 70%. 4. The substrate for a liquid crystal display device according to claim 1, wherein the spacer is made of a polyimide resin. 5. A spacer having an acrylic resin and fixed to a non-display area on a substrate for a liquid crystal display element, wherein said spacer has elasticity with respect to a compressive stress of 0.4 to 0.6 GPa. A liquid crystal display element substrate having a ratio of 0.01 to 80%. 6. The substrate for a liquid crystal display device according to claim 5, wherein the elastic recovery ratio is 0.1 to 60%. 7. The liquid crystal display element substrate according to claim 6, wherein the elastic recovery rate is 1 to 50%. 8. The substrate for a liquid crystal display device according to claim 1, wherein the spacer shape is a circle, an ellipse, a polygon having rounded corners, a cross, a T shape, or an L shape. 9. The liquid crystal display element substrate according to claim 1, wherein the substrate has a plurality of transistors. 10. The substrate for a liquid crystal display device according to claim 1, wherein the substrate is a color filter containing a colorant. 11. The substrate for a liquid crystal display device according to claim 1, wherein the spacer is formed of a single color or a multi-layer of a resin containing a colorant. 12. The substrate for a liquid crystal display device according to claim 1, wherein the spacer has a height of 1 to 9 μm. 13. The substrate for a liquid crystal display device according to claim 1, wherein an area of the spacer in contact with the opposing substrate is 10 to 1000 μm ² per one substrate. 14. A liquid crystal display device according to claim 1, wherein at least one of the liquid crystal display element substrates has a liquid crystal layer sandwiched between two liquid crystal display element substrates. A color liquid crystal display element, which is an element substrate.