JP2001075124A - Manufacture of electrode substrate for liquid crystal display device, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with a spacer function, not to make spacer particles exist in a pixel part and avoid an adverse effect on display quality by forming columnar spacers on the l ight shielding layer on the thin film transistor(TFT) element. SOLUTION: Through holes are formed through a protective layer 13 on a substrate 11 for forming TFT elements. On its full surface an ultraviolet curing adhesive layer 15, which is transparent when it is hardened, is formed. A transferring sheet, which comprises a release layer and a coloring layer 14 formed on a supporting sheet, is stuck to the layer 15. The layer 15 is i rradiated with ultraviolet rays from the rear side of the substrate 11 and made to photoset. Subsequently photoset coloring layer parts are transferred by releasing the supporting sheet. Unhardened adhesive layer parts are removed and pixel wiring of the through hole parts is exposed, is coated with indium tin oxide (ITO) coating liquid and is sintered to form the pixel electrodes 18. A light shielding layer is formed on light nontransmissive parts from which unhardened adhesive layer parts have been removed in advance. Columnar spacers 17 are formed on the light shielding layer on the TFT elements so as to manufacture an electrode substrate 1 having the columnar spacers 17.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode substrate for a liquid crystal display, and more particularly to a method for manufacturing an electrode substrate used in an active matrix type liquid crystal display.
The present invention also relates to a liquid crystal display device using the electrode substrate for a liquid crystal display device manufactured by the manufacturing method.

[0002]

2. Description of the Related Art FIG. 15 is a sectional view schematically showing a part of an example of an active matrix type liquid crystal display device. FIG. 16 is a cross-sectional view schematically showing a part of the thin film transistor element side electrode substrate used in the active matrix type liquid crystal display device in FIG.
As shown in FIGS. 15 and 16, the liquid crystal display device (9) includes a thin film transistor element (hereinafter referred to as TFT element) side electrode substrate (5), an electrode substrate (6), a liquid crystal (3), and a spacer (8). It is configured.

A TFT element side electrode substrate (5) has a TFT element (12) and a pixel electrode (1) on one surface of a transparent substrate (11).
8) An alignment film (16) is formed. Also,
The electrode substrate (6) is composed of a colored layer (14) having a color filter function on one side of a transparent substrate (21), and a facing TFT.
A light-shielding film (27) for concealing the element (12), a transparent conductive film (22), and an alignment film (23) are formed.

In order to keep the thickness of the liquid crystal (3) layer, transparent spherical particles (beads) of glass or synthetic resin called spacers (8) are dispersed in the liquid crystal display (9). Used. Since the spacer is a particle, if the pixel contains a spacer with the liquid crystal, light leaks through the spacer particle during black display, and the liquid crystal material is sealed on the TFT element side. The presence of the spacer particles between the electrode substrate (5) and the electrode substrate (6) disturbs the alignment of the liquid crystal molecules near the spacer particles, causing light leakage at this portion, lowering the contrast of the liquid crystal display device and reducing the display. It has the problem of adversely affecting quality.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem. In a liquid crystal display device, spacer particles for maintaining the thickness of a liquid crystal layer between substrates are provided inside a cell. A method of manufacturing an electrode substrate for a liquid crystal display device, which allows a substrate to have a spacer function for maintaining the thickness of a liquid crystal layer without being present in a pixel portion and enables a liquid crystal display device in which no spacer particles are present in the pixel portion. The task is to provide. Another object of the present invention is to provide a liquid crystal display device using the electrode substrate for a liquid crystal display device manufactured by using the method for manufacturing an electrode substrate for a liquid crystal display device.

[0006]

Means for Solving the Problems The first invention of the present invention is:
In the method of manufacturing an electrode substrate for a liquid crystal display device, 1) a thin film transistor element forming electrode substrate on which at least a thin film transistor element, a gate wiring, a source wiring, a pixel wiring, and an auxiliary capacitance portion are formed on one surface of a transparent substrate; 2) forming a through hole for exposing a pixel wiring according to a predetermined pattern in the protection film on the auxiliary capacitance portion; 3) forming a through hole on the thin film transistor element side of the thin film transistor element formation electrode substrate. A UV-curable adhesive layer that is transparent when cured is formed on the entire surface. 4) The transfer sheet having a release layer and a color layer having a color filter function formed on a support sheet, and the color layer side of the transfer sheet and the thin film transistor. 5) the thin film transistor element is bonded to the element forming electrode substrate with the thin film transistor element side facing the thin film transistor element side; Ultraviolet rays are irradiated by the back exposure from the other surface side of the forming electrode substrate, of the thin-film transistor element formed electrode substrate, a thin film transistor element, the gate line,
After light-curing the adhesive layer of the light-transmitting portion other than the source wiring and the auxiliary capacitance portion, the support sheet is peeled off together with the peeling layer, and the light-curing is performed on the thin film transistor element forming electrode substrate on the thin film transistor element side. Transferring the colored layer portion, and peeling off the uncured colored layer portion; 6) a thin film transistor element on the thin film transistor element side of the thin film transistor element forming electrode substrate;
Removing the uncured adhesive layer portion of the light-impermeable portion such as the source wiring and the auxiliary capacitance portion to expose the pixel wiring for the through hole; and 7) on the thin film transistor element side of the thin film transistor element forming electrode substrate 8) Applying and baking an ITO coating solution on the entire surface to form a transparent conductive film. 8) The transparent conductive film is patterned into a predetermined shape, and is electrically connected to the pixel wiring through the through hole. 9) forming a light-shielding film on the light-impermeable portion from which the uncured adhesive layer portion has been removed, and forming a columnar spacer on the light-shielding film on the thin film transistor element; A method for manufacturing an electrode substrate for a liquid crystal display device, comprising manufacturing an electrode substrate for a liquid crystal display device having a spacer.

The present invention also relates to a method of manufacturing an electrode substrate for a liquid crystal display device according to the present invention, wherein the light-shielding film has a high insulating property.

Next, a second invention of the present invention is a liquid crystal display device using the electrode substrate for a liquid crystal display device manufactured by the method for manufacturing an electrode substrate for a liquid crystal display device according to the above invention. .

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention will be described in detail based on one embodiment. FIG. 1 is a cross-sectional view schematically showing a part of an electrode substrate for a liquid crystal display device manufactured by an embodiment of the method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention. FIG. 2 is a cross-sectional view schematically showing a part of an example of a liquid crystal display device using the electrode substrate for a liquid crystal display device shown in FIG.

As shown in FIG. 1, an electrode substrate (1) for a liquid crystal display device has a TFT element (12), a protective film (13), an adhesive layer (15), a color on one side of a transparent substrate (11). The coloring layer (14) having a filter function and the pixel electrode (1
8), an alignment film (16), and a columnar spacer (17) are formed. As shown in FIG. 2, the liquid crystal display device (4) using the electrode substrate for a liquid crystal display device (1) shown in FIG. 1 comprises an electrode substrate for a liquid crystal display device (1), an electrode substrate (2), and It is composed of a liquid crystal (3). The electrode substrate (2) has a transparent conductive film (2) on one side of the transparent substrate (21).
2) An alignment film (23) is formed.

As shown in FIGS. 1 and 2, in a liquid crystal display device (4) using an electrode substrate for a liquid crystal display device (1) manufactured by a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention. The columnar spacer (17) has a spacer function for maintaining the thickness of the liquid crystal layer without providing spacer particles for maintaining the thickness of the liquid crystal layer between the substrates in the pixel portion inside the cell. This enables a liquid crystal display device in which no spacer particles are present.

FIGS. 3 (a), 3 (b) and 3 (c) are illustrations of a transfer sheet used in the method of manufacturing an electrode substrate for a liquid crystal display device according to the present invention. 3A is a plan view of the transfer sheet (30), FIG. 3B is a sectional view taken along line XX ′ in FIG. 3A, and FIG. 3C is a sectional view taken along line YY ′ in FIG.

As shown in FIGS. 3 (a), 3 (b) and 3 (c), the transfer sheet (30) has a release layer (32) on a support sheet (31) and a colored layer (1) having a color filter function.
4) is formed. A large number of colored layers (14) having a color filter function are regularly arranged in a stripe shape for color display, for example, red (R), green (G), and blue (B). The coloring layer (14) is formed of a pigment-dispersed photoresist, a printing ink, a dyeing resin, a multi-layer inorganic material, or the like.

4 to 14 are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention. FIG.
(A), (b), and (c) are thin film transistor element forming electrode substrates (hereinafter referred to as TFT element forming electrodes) used for manufacturing a liquid crystal display electrode substrate manufactured by the method for manufacturing a liquid crystal display electrode substrate according to the present invention. FIG. 4A is a plan view of a TFT element forming electrode substrate (40), FIG. 4B is a cross-sectional view taken along line XX ′ in FIG.
FIG. 3 is a sectional view taken along the line YY ′ in FIG.

As shown in FIGS. 4A, 4B and 4C, the TFT element forming electrode substrate (40) is made of a transparent substrate (1).
TFT element (12) and gate wiring (4)
1), a source wiring (42), a pixel wiring (43), and an auxiliary capacitance section (44) are formed. The pitch (P) and width (W) of the source wiring (42) in FIG. 4 are the same as those of the colored layer (14) on the transfer sheet in FIG.
Corresponding to the pitch (P) and the width (W). The TFT element (12) has a gate electrode (45), an insulating film (19), a source electrode (46), and a silicon (4).
7) and a drain electrode (48).

First, as shown in FIGS. 4A, 4B and 4C, a protective film (49) is formed on the entire surface of the TFT element forming electrode substrate (40) on the TFT element side. Then, as shown in FIG. 5, through holes (5) are formed in the protective film (49) on the auxiliary capacitance portion (44) by a photolithography method, a dry etching method, or the like, as shown in FIG.
1) is formed, and a part of the pixel wiring (43) is exposed from the protective film.

Next, as shown in FIG. 6, an adhesive layer (15) made of a solventless UV-curable adhesive is formed on the entire surface of the TFT element forming electrode substrate (40) on the TFT element side. It is important to use a non-solvent type ultraviolet curable adhesive which is transparent when cured and transmits light. Next, as shown in FIG. 7, the transfer sheet (30) is divided into the width (W) of the source wiring (42) in FIG. 4 and the colored layer (14) on the transfer sheet in FIG.
TF while controlling the position to correspond to the width (W) of
It is superposed on the T element forming electrode substrate (40). At this time, the adhesive layer (1) of the TFT element forming electrode substrate (40) is formed.
The surface on which 5) is formed and the surface on which the colored layer (14) of the transfer sheet (30) is formed are opposed to each other.

Next, as shown in FIG. 8, ultraviolet rays (81) are irradiated from the side opposite to the TFT element side of the TFT element forming electrode substrate (40) to form the TFT element, gate wiring, source wiring, auxiliary capacitance part, etc. The adhesive layer (15) of the light transmitting portion other than the above is light-cured. Then, as shown in FIG.
The support sheet (31) is peeled off together with the release layer (32),
The photocured colored layer (14) is transferred to the TFT element side of the TFT element forming electrode substrate (40), and the uncured colored layer is peeled off.

Next, as shown in FIG. 10, the uncured adhesion of the light-impermeable portions such as the TFT element, the gate wiring, the source wiring, and the auxiliary capacitance section on the TFT element side of the TFT element forming electrode substrate (40). The agent layer (15) is removed to expose the pixel wiring (43) for the through hole. Then
As shown in FIG. 11, the TFT element forming electrode substrate (40)
A transparent conductive film (28) is formed by applying and baking an ITO coating solution on the entire surface on the TFT element side.

Next, as shown in FIG. 12, the transparent conductive film is patterned into a predetermined shape to form a pixel electrode (18) made of the transparent conductive film electrically connected to the pixel wiring (43) by through holes. I do. Next, as shown in FIG. 13, a light-shielding film (27) is formed on the light-impermeable portion from which the uncured adhesive layer portion has been removed, and subsequently, as shown in FIG. 14, the TFT element (12) A columnar spacer (17) is formed on the upper light shielding film. Through the above steps, an electrode substrate for a liquid crystal display device having a columnar spacer is manufactured.

As the transparent substrate in the present invention, glass, preferably a glass having a small coefficient of thermal expansion containing little or no alkali metal element is used. Its thickness is
For example, it is about 0.5 to 1.1 mm.

The transfer base is a continuous metal plate or metal foil, and has a plate thickness of 0.15 mm or less, preferably about 0.06 to 0.09, and is made of a material such as a transparent substrate as a transfer object. Metals having approximately equal coefficients of thermal expansion are preferred. The transparent glass substrate used for the liquid crystal display device has a coefficient of thermal expansion of 40 ×
Since it is a glass having a low expansion coefficient of about 10 ⁻⁷ / ° C., the metal to be used is an iron-nickel alloy, for example, 42 alloy (nickel 42% by weight, balance iron), amber (nickel 36
Wt%, trace amount of manganese, balance iron) etc.
This is convenient because it is about 0 × 10 ⁻⁷ / ° C. Iron-nickel alloys are also suitable in that they hardly rust in the air and have good storage stability.

The release layer is a polymer film having resistance to an organic solvent, and provides an effect of smoothing the surface of the transfer base and elasticity for maintaining the adhesion between the transparent glass substrate and the transfer base during transfer. . The thickness is preferably 4.5 μm or more and 5.5 μm or less. It is preferable that the release layer has flexibility in terms of transfer suitability. On the other hand, in view of the original suitability of the release layer, it is desirable that the surface is inert and the film hardness is high.

Specifically, a film obtained by coating and drying casein, polyvinyl alcohol, hydroxyethylcellulose, etc. with a water-soluble resin having organic solvent resistance, and a polyurethane resin and various rubber resins as elastic resins can be given. However, it is not limited to these resins. It is also effective to add a silicone-based or fluorine-based surfactant for the purpose of improving releasability, and the transfer base can exhibit its original function only when integrated with the release layer.

The coloring layer can be applied by a dyeing method, a pigment dispersion method, a printing method, or the like. The dyeing method is a dyeable resin, for example, gelatin,
Dichromic acid is added to low molecular weight gelatin, glue, casein, etc. to form a photosensitive resin, pattern irradiation is performed using active light, development is performed, and then dyeing is performed with an anionic dye to perform anti-staining treatment. To form red, green and blue. Further, a similar colored layer can be formed using a dyeable synthetic resin having photosensitivity having a cationic group such as an amide group or an amino group.

In the pigment dispersion method, a colored resin is formed by repeating the steps of coating, exposing, developing and heating a photosensitive resin in which a pigment of a desired hue is dispersed in advance. The printing method is a method of forming a color coloring layer by sequentially printing red, green, and blue inks on a substrate, for example, mainly by lithographic offset or intaglio offset printing.

The light-shielding film and the columnar spacer in the present invention are preferably highly insulating. The high insulating property prevents leakage between the electrode substrates of the liquid crystal display device and improves the display quality.

[0028]

The present invention will be described in detail with reference to the following examples. <Example 1> (Preparation of transfer sheet) 110 μm thick as support sheet
42 alloy (iron-nickel alloy, nickel 42% by weight,
The balance iron) was used. Alignment marks for forming the respective colored layers, positioning between the colored layers and the TFT element forming electrode substrate, and the like were formed on predetermined portions of the support sheet by photolithography.

Next, a release layer made of photo-cured polyvinyl alcohol, which adheres well to the support sheet and has good releasability from the colored layer, has a thickness of about 5 μm and a surface smoothness of 0.0
It was formed to about 5 μm. A colored layer was formed on the cured release layer by a pigment dispersion method using a known photolithography method to obtain a transfer sheet.

(Preparation of Electrode Substrate for Liquid Crystal Display) A TFT having a TFT element, a gate wiring, a source wiring, a pixel wiring, and an auxiliary capacitor formed on one surface of a transparent substrate by a known method.
An FT element forming electrode substrate was used. First, a protective film was formed by depositing form SiO ₂ on the entire surface of the TFT element formation electrode substrate.

Next, after applying a photosensitive resist (trade name “AZ4620”, manufactured by Hoechst) on the protective film, the protective film is formed from the photosensitive resist in the region of the auxiliary capacitance portion by photolithography according to a predetermined pattern. Was partially exposed. Next, using a dry etching apparatus (trade name “Drytec 384T” manufactured by Lam Research Co., Ltd.), pressure 150 mTorr, output 700 W, CHF ₃ gas amount 1
Under the condition of 00SCCM, dry etching was performed on the protective film exposed from the photosensitive resist. Thereafter, the photosensitive resist was peeled off, and a through-hole exposing a part of the pixel electrode was formed in the protective film according to a predetermined pattern.

Next, an adhesive layer was applied and formed on the entire surface of the TFT element forming electrode substrate. The adhesive used was a resin comprising a resin having an ethylenically unsaturated group and a carboxyl group in the molecule, a diluting monomer, a photosensitizer, a thermosetting component, and an additive.

Resins having an ethylenically unsaturated group and a carboxyl group in the molecule have a double bond equivalent of 30 from the viewpoint of sensitivity.
The carboxyl group must be in the range of 50 to 150 as the resin acid value from the viewpoint of developability. If the acid value is 50 or less, the developability will be reduced, resulting in residual development residue and reduced edge cut. On the other hand, if the acid value is 150 or more, there is a problem that swelling occurs at the time of development and a clear pattern cannot be obtained. Further, the molecular weight of the resin is suitably in the range of 1,000 to 100,000, and when the molecular weight is 1,000 or less, the sensitivity is lowered.
If it is more than 00, the developability is reduced.

As the resin, an acrylic copolymer of a monomer having a glycidyl group and an ethylenically unsaturated group such as glycidyl methacrylate (GMA) and a monomer having an ethylenically unsaturated group such as acrylic acid and a carboxyl group are used. After addition of an acid anhydride such as phthalic anhydride or tetrahydrophthalic anhydride, or an acrylic copolymer of a monomer having an ethylenically unsaturated group and a carboxyl group such as acrylic acid. And a resin to which a monomer having a glycidyl group and an ethylenically unsaturated group is added. Also, after adding a carboxylic acid having an ethylenically unsaturated group such as acrylic acid to an epoxy resin such as a phenol novolak resin or a cresol novolak resin or a bisphenol type, phthalic anhydride,
Those to which tetrahydrophthalic anhydride has been added can also be used.

The diluent monomer should have a boiling point of 200 ° C. or higher so as not to cause foaming or the like at the time of curing, and should be able to be diluted to an appropriate viscosity because of workability at the time of bonding. ) Multifunctional monomers such as acrylates, trifunctional monomers such as pentaerythritol tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, trimethylolpropanetri (meth) acrylate, 1.6 hexanediol di (meth) acrylate, Bifunctional monomers such as neopentyl glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecyl (meth) acrylate, isobonyl (meth) acrylate, lauryl (meth) Monofunctional monomers such as acrylate, hydroxyethyl (meth) acrylate, and 2-acryloyloxyethyl monophthalate; polyol compounds having two or more hydroxyl groups; urethane acrylates and epoxy acrylates comprising isocyanate compounds and (meth) acrylates having hydroxyl groups; These can be used in appropriate combination.

The photosensitizer is not particularly restricted but includes benzophenone, diethylaminobenzophenone, methyl benzoylbenzoate, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, Thioxanthone, diethylthioxanthone, 2
-Methyl {4- (methylthio) phenyl} -2-morpholino-1-propanone; the amount of addition is preferably 0.1 to 20 parts by weight based on the total amount of the resin and the diluent monomer.

Examples of the additives include polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether; adhesives such as silane coupling agents and titanium coupling agents; and thermosetting components such as epoxy resins, polyols and melamine resins. When there is no thermosetting component among them, a large amount of carboxylic acid groups remain in the cured resin, and the water resistance is reduced. The addition amount is preferably 1/2 equivalent or more based on the carboxylic acid in the resin.

The preparation of the adhesive was performed as follows.
A polymer having a molecular weight of 20,000 was obtained using ADVN (manufactured by Otsuka Chemical Co., Ltd.) under the nitrogen atmosphere with 40 g of GMA, 60 g of MMA and 200 g of acetone. After adding and reacting 20 g of acrylic acid and 0.2 g of benzyldimethylamine to this polymer solution, 25 g of tetrahydrophthalic anhydride was added thereto for reaction, precipitated and precipitated with cyclohexane, and dried to obtain 130 g of a white powder. The molecular weight of the resin of this powder is 3
5000, acid value was 100. 50 g of this resin
MP3A 50 g, hydroxyethyl methacrylate 40
g, 1,6-hexanediol dimethacrylate 40
g, biscolate # 2000 (manufactured by Osaka Organic Chemical Co., Ltd.)
10 g, Irgacure 184 (manufactured by Ciba Geigy) 10
g, methoquinone 0.1 g, and glycidoxypropyltrimethoxysilane 10 g were added and dissolved to obtain an adhesive.

After the adhesive layer is applied to the entire surface of the TFT element forming electrode substrate, the transfer sheet is superimposed so that the TFT element forming surface and the colored layer surface face each other while positioning the transfer sheet. After pressing the TFT element forming electrode substrate and the transfer sheet at a pressure of 5 kg / cm ² with a roll press, ultraviolet rays are irradiated from the side opposite to the TFT element forming surface to irradiate the adhesive excluding the elements and the wiring parts. After curing, the colored layer was transferred to the TFT element forming electrode substrate. At this time, the portion of the adhesive layer on the TFT element and the wiring is not exposed to light and does not harden because the TFT element and the wiring shield the ultraviolet rays irradiated.

Next, the support sheet is removed together with the release layer, and the TFT element forming electrode substrate is washed with an alkaline solution or the like.
The unexposed and uncured portions, that is, the adhesive on the TFT element and the wiring were removed. As a result, the unexposed and uncured adhesive layer on the TFT element and the wiring is removed by washing, and the surfaces of the TFT element and the wiring appear. Next, an ITO coating solution was applied and baked to form a transparent conductive film, which was etched using a photolithography method. Thereby, a pixel electrode patterned into a predetermined shape was formed on the colored layer. The pixel electrode is electrically connected to the pixel wiring through a through hole.

Next, a light-shielding film was formed on the TFT element region and the wiring by using photolithography. continue,
A columnar spacer was formed on the light-shielding film on the TFT element, and an electrode substrate for a liquid crystal display device having the columnar spacer was obtained.
The formation of the light-shielding film and the columnar spacers is performed by uniformly applying a black photosensitive resin composition by using a spinner method to form a black resin layer, exposing by ultraviolet irradiation using a mask pattern, and heating at a temperature of 70 ° C to 150 ° C. The heat treatment and the development treatment utilizing the catalytic reaction of the acid were carried out for 15 seconds to 5 minutes.

The black photosensitive resin composition used is as follows and has a high insulating property. The composition is composed of a resin material, a crosslinking agent, a photoacid generator, and a polymer-grafted titanium oxide black. Become.

The resin-based material is a polymer compound containing an OH group which can be a cross-linking point and soluble in an alkaline aqueous solution.
Homopolymers or copolymers of phenols represented by p-hydroxystyrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid and other monomers containing OH groups Is used. Other monomers that can be used for copolymerization include styrene, phenylmaleimide,
Examples include methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and benzyl methacrylate. These resin materials are 10 to 5
It is used in an amount of 5% by weight, preferably 17-55% by weight. If the amount is too small, problems such as deterioration of the photosensitive function, deterioration of the pattern shape due to aggregation of titanium oxide, and insufficient film strength and adhesion occur. If too large, the light-shielding properties are insufficient.

Examples of the crosslinking agent include methylolated urea, urea resin, methylolated melamine, butyrolized melamine,
It is possible to use methylolated guanamine or an alkyl ether of these compounds. Alkyl ethers are more preferred because of their excellent thermal stability.
The alkyl group of the alkyl ether has 1 to 1 carbon atoms.
5 alkyl groups are preferred. In particular, as this alkyl ether compound, an alkyl ether compound of hexamethylolmelamine, which is excellent in sensitivity, is more preferable. Further, a compound having two or more epoxy groups can also be used. These crosslinkers are present in 4 to 17% by weight, preferably 7%.
It is used in the range of １５15% by weight. If the amount is too small, the photosensitive characteristics are hindered. If the amount is too large, the light-shielding property is insufficient.

As the photoacid generator, there can be used a trihalomethyl group-containing triazine derivative or an onium salt which has an absorption in a wavelength range included in light emission of a light source and generates an acid by light absorption. Examples of trihalomethyl group-containing triazine derivatives include, for example, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl)
-S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 ′
-Methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-
Triazine and the like can be mentioned.

Other onium salts include, for example,
Diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate,
Diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate,
Methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate,
Methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenyliodonium-p-toluenesulfonate, bis (4
-Tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl)
Iodonium hexafluorophosphonate, bis (4-
tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium -Diaryliodonium salts such as p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, Phenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonate Arm tetrafluoroborate, 4-
Methoxyphenyl diphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-triene Sulfonate, 4-
Phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, And triarylsulfonium salts such as 4-phenylthiophenyldiphenyl-p-toluenesulfonate.

These photoacid generators may be used alone or in combination. For example, a combination of a light absorber and an acid generator can be used. The addition amount is preferably 0.5 to 40% by weight based on the resin material. This is 4
If it is added in excess of 0% by weight, the amount of acid generated is too large, and the acid diffuses into unexposed areas due to heating after pattern exposure, causing a cross-linking reaction and causing a reduction in resolution.
On the other hand, when the addition amount is less than 0.5% by weight, the amount of acid generated is insufficient, the crosslinking reaction does not proceed sufficiently, and a pattern cannot be formed.

The polymer compound used for grafting titanium oxide black has a group which can easily react with a functional group present on the surface of titanium oxide black.
Specific examples of this group include an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, an isocyanate group, a vinyl group, an acryl group, a methacryl group, a silicon-based hydrolyzable group, and an amino group. In the polymer compound, these groups are represented by 1 in the molecule.
It is necessary to have one or more species. In particular, in terms of reactivity with the functional group on the surface of titanium oxide black, it has one or more groups selected from an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, and an isocyanate group. High molecular compounds are preferred. More preferably, aziridine group, oxazoline group, N
One or two selected from -hydroxyalkylamide groups
It is a polymer compound having more than one kind of groups.

When reacting titanium oxide black with a polymer compound, substances such as polymer components, monomers, and organic solvents other than the polymer compound may be present in the reaction system as long as the reaction is not inhibited. The polymer compound is 10 to 100% by weight, preferably 20% by weight of titanium oxide black.
６０60% by weight. When the content is less than 10% by weight, the effect of grafting, that is, the improvement of the film strength is not obtained.
If the content is more than 10% by weight, the photosensitivity is impaired or the optical density is insufficient.

The pH of the titanium oxide black is preferably 7 or less, more preferably 5 or less. When the pH is 7 or more, the effect of grafting, that is, improvement in film strength is not recognized. These materials are kneaded using a disperser such as a two-roll mill, a three-roll mill, a sand mill, and a paint conditioner to obtain a black photosensitive resin composition. Furthermore,
Ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, ethyl carbitol acetate, diglyme as a diluting solvent to improve workability at the time of dispersion
Organic solvents such as cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and lactic acid esters may be used.

As described above, a high-sensitivity black photosensitive resin composition can be obtained by using a resin material, a crosslinking agent and a photoacid generator. Further, by using the grafted titanium oxide black material, a light-shielding film having excellent film strength and high light-shielding properties can be obtained. By using a photosensitive resin composition that crosslinks using an acid generated from a photoacid generator, the slope of the sensitivity characteristic curve increases, and the residual film ratio after development suddenly increases in a region above a certain exposure amount. Therefore, an effect of obtaining a predetermined film thickness with a low exposure amount is exhibited.

By the above action, it is not necessary to cure the inside of the black photosensitive resin layer with a large amount of ultraviolet rays as in the case of using the conventional radical polymerization type black photosensitive resin composition. Column spacers could be formed. Note that the embodiment of the present invention is not limited to the above embodiment, and the material to be used, the film thickness, the color of the coloring layer,
It goes without saying that various conditions such as the structure of the element can be changed.

[0053]

According to the present invention, in a method of manufacturing an electrode substrate for a liquid crystal display device, a protective film is formed on an electrode substrate on which a thin film transistor element is formed, a through hole is formed in the protective film on an auxiliary capacitance portion, and ultraviolet curing is performed. Forming a mold adhesive layer, bonding a transfer sheet on which a release layer and a colored layer are formed on a support sheet so as to face each other, irradiating ultraviolet rays by back exposure, and photo-curing the adhesive layer in the light transmitting portion After that, the support sheet is peeled off together with the release layer, the photocured colored layer portion is transferred, the uncured colored layer portion is peeled off, and the uncured adhesive layer portion of the light impermeable portion is removed. A transparent conductive film is formed by exposing the pixel wiring for the through hole, applying an ITO coating solution and baking to form a transparent conductive film, patterning the transparent conductive film, and electrically connecting the pixel wiring with the pixel wiring through the through hole. Forming pixel electrodes A light-shielding film is formed on the light-impermeable portion, a columnar spacer is formed on the light-shielding film on the thin film transistor element, and a liquid crystal display substrate having the columnar spacer is manufactured. The spacer function to maintain the thickness of the liquid crystal layer is provided on the substrate without the spacer particles for maintaining the layer thickness in the pixel portion inside the cell, and the spacer particles are not present in the pixel portion. An electrode for a liquid crystal display device that enables a liquid crystal display device that does not have the problem that the arrangement of liquid crystal molecules near the particles is disturbed, light leakage occurs at this portion, and the contrast of the liquid crystal display device is reduced and display quality is not adversely affected. This is a method of manufacturing a substrate.

Further, the present invention is a liquid crystal display device using the electrode substrate for a liquid crystal display device manufactured by the above-mentioned method for manufacturing an electrode substrate for a liquid crystal display device, so that the thickness of the liquid crystal layer between the substrates is maintained. The spacer functions to keep the thickness of the liquid crystal layer on the substrate without having the spacer particles in the pixel portion inside the cell, and the spacer particles do not exist in the pixel portion, that is, the arrangement of the liquid crystal molecules near the spacer particles. The liquid crystal display device does not have the problem that light leakage occurs at this portion, the contrast of the liquid crystal display device is reduced, and the display quality is adversely affected.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically illustrating a part of an electrode substrate for a liquid crystal display device manufactured according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view schematically showing a part of an example of a liquid crystal display device using the electrode substrate for a liquid crystal display device shown in FIG.

FIGS. 3A, 3B, and 3C are explanatory views of a transfer sheet used in the method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 4A, 4B and 4C are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 5A, 5B and 5C are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 6 (a), (b) and (c) are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 7A, 7B and 7C are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 8A, 8B, and 8C are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 9A, 9B, and 9C are explanatory views illustrating a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 10A, 10B, and 10C are explanatory views illustrating a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 11 (a), (b) and (c) are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 12 (a), (b) and (c) are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

13 (a), (b) and (c) are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIGS. 14 (a), (b) and (c) are explanatory views showing a method for manufacturing an electrode substrate for a liquid crystal display device according to the present invention.

FIG. 15 is a cross-sectional view schematically illustrating a part of an example of an active matrix liquid crystal display device.

16 is a cross-sectional view schematically showing a part of a thin film transistor element side electrode substrate used in the active matrix type liquid crystal display device in FIG.

[Explanation of symbols]

 1 electrode substrate for liquid crystal display 2 electrode substrate 3 liquid crystal 4 liquid crystal display 5 thin film transistor element side electrode substrate 6 electrode substrate in conventional method 8 spacer 9 in conventional method Liquid crystal display device 11, 21 Transparent substrate 12 TFT element 13, 49 Protective film 14 Coloring layer 15 Adhesive layer 16, 23 Alignment film 17 Columnar spacer 18 Pixel electrode 19 insulating film 22, 28 transparent conductive film 27 light shielding film 30 transfer sheet 31 support sheet 32 release layer 40 TFT element forming electrode substrate 41 gate wiring 42 source Wiring 43 pixel wiring 44 auxiliary capacitance 45 gate electrode 46 source electrode 47 silicon 48 drain electrode 51 through hole 81 ultraviolet ray R red G ‥‥ green B ‥‥ blue

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinji Ito 1-5-1, Taito, Taito-ku, Tokyo Inside Toppan Printing Co., Ltd. (72) Inventor Mizunin Tani 1-1-1, Taito, Taito-ku, Tokyo F Term in Toppan Printing Co., Ltd. (Reference) 2H089 LA09 LA16 MA04X MA05X NA05 NA08 NA14 NA15 PA05 QA12 QA14 QA15 TA09 TA12 TA13 2H092 HA28 JA24 JA46 JB69 MA04 MA10 MA13 MA19 MA37 MA42 PA03 PA08 PA09 5C094 AA03 AAA AA A08 BA43 CA19 CA24 DA13 DB04 EA04 EA05 EB02 EC03 ED03 FA01 FB01 FB15 GB10

Claims (3)

[Claims] 1. A method of manufacturing an electrode substrate for a liquid crystal display device, wherein: 1) a thin film transistor element forming electrode substrate in which at least a thin film transistor element, a gate wiring, a source wiring, a pixel wiring, and an auxiliary capacitance portion are formed on one surface of a transparent substrate. 2) forming a protective film on the thin film transistor element side; 2) forming a through hole for exposing a pixel wiring according to a predetermined pattern in the protective film on the auxiliary capacitance portion; and 3) forming a through hole for the thin film transistor element forming electrode substrate. A UV-curable adhesive layer that is transparent when cured is formed on the entire surface on the thin film transistor element side. 4) The coloring of the transfer sheet in which a release layer and a colored layer having a color filter function are formed on a support sheet 5) the thin film transistor is bonded to the thin film transistor forming electrode substrate such that the layer side faces the thin film transistor device side; Ultraviolet rays are irradiated by the back exposure from the other surface side of the Njisuta element forming the electrode substrate, of the thin-film transistor element formed electrode substrate, a thin film transistor element, the gate line,
After light-curing the adhesive layer of the light-transmitting portion other than the source wiring and the auxiliary capacitance portion, the support sheet is peeled off together with the peeling layer, and the light-curing is performed on the thin film transistor element forming electrode substrate on the thin film transistor element side. Transferring the colored layer portion, and peeling off the uncured colored layer portion; 6) a thin film transistor element on the thin film transistor element side of the thin film transistor element forming electrode substrate;
Removing the uncured adhesive layer portion of the light-impermeable portion such as the source wiring and the auxiliary capacitance portion to expose the pixel wiring for the through hole; and 7) on the thin film transistor element side of the thin film transistor element forming electrode substrate 8) Applying and baking an ITO coating solution on the entire surface to form a transparent conductive film. 8) The transparent conductive film is patterned into a predetermined shape, and is electrically connected to the pixel wiring through the through hole. 9) forming a light-shielding film on the light-impermeable portion from which the uncured adhesive layer portion has been removed, and forming a columnar spacer on the light-shielding film on the thin film transistor element; A method for manufacturing an electrode substrate for a liquid crystal display device, comprising manufacturing an electrode substrate for a liquid crystal display device having a spacer. 2. The method according to claim 1, wherein the light-shielding film has a high insulating property. 3. A liquid crystal display device using an electrode substrate for a liquid crystal display device manufactured by the method for manufacturing an electrode substrate for a liquid crystal display device according to claim 1.