JP2003241199A - Photosetting resin composition, substrate for liquid crystal panel, and liquid crystal panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate for liquid crystal panel with which a uniform cell gap can be maintained, a liquid crystal panel which uses the substrate for liquid crystal panel and is excellent in display quality and a forming material suitable for columnar spacers. <P>SOLUTION: The substrate for the liquid crystal panel (a color filter 103) comprises a plurality of the columnar spacers 12 arranged on non-displaying regions of a substrate 5. The columnar spacers have 60% or higher elastic deformation with respect to 2.0 GPa compressive load at room temperature. Also, at least one out of the display side substrate and the liquid crystal driving side substrate constituting the liquid crystal panel is the substrate for the liquid crystal panel. The columnar spacers are formed by a photosetting resin composition containing a polyfunctional acrylate monomer, a polymer and a photopolymerization initiator and having 50 wt.% or higher content of the polyfunctional acrylate monomer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal panel substrate capable of maintaining a uniform cell gap, and a liquid crystal panel excellent in display quality using the liquid crystal panel substrate.

[0002]

2. Description of the Related Art In a liquid crystal panel, a display side substrate and a liquid crystal driving side substrate are opposed to each other, and a liquid crystal compound is sealed between them to form a thin liquid crystal layer. Is electrically controlled to selectively change the amount of transmitted light or reflected light of the display-side substrate to perform display.

The liquid crystal panel has a static drive system,
There are various driving methods such as a simple matrix method and an active matrix method, but in recent years, color liquid crystal display devices using an active matrix method or a simple matrix method liquid crystal panel have been rapidly used as a flat display of a personal computer or a portable information terminal. It is becoming popular.

FIG. 1 shows an example of the structure of an active matrix type liquid crystal panel. In the liquid crystal panel 101, a color filter 1 which is a display side substrate and a TFT array substrate 2 which is a liquid crystal drive side substrate are opposed to each other to provide a gap portion 3 of about 1 to 10 μm, and the liquid crystal L is filled in the gap portion 3. Then
It has a structure in which the periphery thereof is sealed with a sealing material 4. The color filter 1 includes a black matrix layer 6 formed on a transparent substrate 5 in a predetermined pattern to shield the boundaries between pixels, and a plurality of colors (usually red (R ), Green (G), and blue (B) three primary colors) are arranged in a predetermined order, or a pixel section using a hologram these days, a protective film 8, and a transparent electrode film 9 are formed on a transparent substrate. The structure is such that the layers are stacked in this order from the closer side. On the other hand, the TFT array substrate 2 is a TFT on a transparent substrate.
It has a structure in which elements are arranged and a transparent electrode film is provided (not shown). An alignment film 10 is provided on the inner surface of the color filter 1 and the TFT array substrate 2 facing the color filter 1. Then, a color image is obtained by controlling the light transmittance of the liquid crystal layer behind the pixels colored in each color.

The thickness of the gap portion 3, that is, the cell gap (gap distance between the display side substrate and the liquid crystal drive side substrate) is the thickness of the liquid crystal layer itself, and prevents display unevenness such as color unevenness and contrast unevenness, and makes it uniform. In order to impart good display performance such as display, high-speed response, high contrast ratio, and wide viewing angle to the color liquid crystal display device, it is necessary to maintain the cell gap constant and uniform.

As a method of maintaining the cell gap, spherical or rod-shaped particles 11 of glass, alumina, plastic or the like having a certain size are used as spacers in the gap portion 3.
There is a method of injecting a liquid crystal in which a large number of cells are scattered, the color filter 1 and the TFT array substrate 2 are bonded together. In this method, the cell gap is determined and maintained by the size of the spacer.

However, in the method in which particles are scattered as spacers in the gap, the distribution of spacers tends to be biased.
Also, the particulate spacers are randomly scattered regardless of whether they are behind the black matrix layer 6 or behind the pixels. When the spacer exists in the display area, that is, in the pixel portion, after the light of the backlight is transmitted through the spacer portion, the alignment of the liquid crystal around the spacer is disturbed, or only the liquid crystal around the spacer can be controlled by turning the voltage on and off. There is a problem that the display quality such as the contrast ratio is deteriorated due to the trouble such as being disabled.

Generally, if the scattered amount (density) of the spacers is increased, the spacers are evenly distributed over the entire surface area of the gap portion and the variation of the cell gap is reduced. However, when the scattered amount of the spacers is increased, the display area is increased. Since the number of spacers existing in the same also increases, the above problems become apparent and the display quality is remarkably deteriorated.

As a method of solving the problem of the particulate spacers, as shown in FIG. 2, in the area (non-display area) on the inner surface side of the color filter 1 which overlaps with the position where the black matrix layer 6 is formed. The columnar spacers 12 having a height corresponding to the cell gap have been formed. Column spacer 12
Is by applying a photocurable resin to a uniform thickness on the transparent substrate of the color filter, and by pattern-exposing the obtained coating film by photolithography and curing it.
It is formed in the formation region of the black matrix layer, that is, in the non-display region.

Generally, the photocurable resin used for photolithography is a composition containing a monomer, a polymer and a photopolymerization initiator. However, the columnar spacers formed using such a conventional photo-curable resin are plastically deformed under high temperature and high pressure at the time of assembling (cell pressure bonding) of the color filter and the TFT array substrate to form a cell gap of a predetermined distance. There is a problem in that the function as a spacer is hindered, for example, it becomes impossible to maintain the uniformity and display unevenness occurs.

Further, the cured resin columnar spacer is plastically deformed by an external impact or a pressing force even after the color filter and the TFT array substrate are assembled to form a liquid crystal panel, and the cell gap varies to cause display unevenness. For example, the function as a spacer may be impaired.

If the hardness of the columnar spacers is increased to prevent such plastic deformation, a wide practical temperature range (-2
There is a problem that the liquid crystal layer cannot follow the contraction and expansion of the liquid crystal at 0 ° C. to + 40 ° C. and foaming occurs in the liquid crystal layer, resulting in deterioration of quality display such as color loss and color unevenness.

In order to form and maintain the cell gap accurately and uniformly by the columnar spacer, it is necessary to solve the above problems.

Further, in recent years, the area of liquid crystal display devices has been increased, and the necessity of maintaining a uniform cell gap over the entire area of a wide substrate has increased. When the substrate area becomes large, the substrate will be distorted even by a relatively small external force, so that it has been necessary to prevent the gap variation due to the strain. Further, in recent years, since the thickness of the liquid crystal layer, that is, the cell gap has been narrowed in order to improve the display response, it is necessary to accurately maintain the narrow gap.

As described above, with the recent enlargement of the display area and the narrowing of the cell gap in the liquid crystal display device, even a slight loss of the uniformity of the cell gap has a great influence on the display performance, resulting in uneven display. The display quality is likely to deteriorate. Therefore, the requirements for accuracy and uniformity of the cell gap are becoming more and more stringent.

Further, in recent years, in order to improve productivity by simplifying the steps of assembling the color filter and the TFT array substrate (cell pressure bonding) by eliminating heating steps and slow cooling steps, cell pressure bonding is performed at room temperature (room temperature). Cell crimping method) has been proposed.

Further, in order to improve the productivity of the cell crimping process, the one drop fill method (One Drop Fill Technolog) is used.
y: ODF method) has been proposed (1354 SID 01 DIGEST, 5
6.3: Development of One Drop Fill Technology for AM
-LCDs (H. Kamiya et al.)). In this method, a predetermined amount of liquid crystal droplets are dropped on the liquid crystal sealing surface of a liquid crystal panel substrate such as a color filter or a TFT array substrate, and the other liquid crystal panel substrate is kept under vacuum to maintain a predetermined cell gap. Face each other as they can and stick them together.
This method can simplify the process as compared with the conventional cell pressure bonding process. Further, in the conventional cell pressure bonding process, the color filter and the TFT array substrate are faced to each other in a state where a predetermined cell gap can be maintained and bonded, and then the capillary phenomenon and the inside / outside of the cell gap are introduced from the filling port provided at one end of the bonded body. Although the liquid crystal is filled and sealed in the cell gap by utilizing the pressure difference of No. 1, it becomes difficult to fill the liquid crystal smoothly with the expansion of the display area and the narrowing of the cell gap described above. is there. On the other hand, in the ODF method, even if the liquid crystal panel substrate has a large area and the cell gap is narrowed,
Liquid crystal can be easily enclosed. This new productive method may become mainstream in the future.

[0018]

SUMMARY OF THE INVENTION The present invention has been accomplished in view of such circumstances, and the first object thereof is to provide a sufficient hardness that plastic deformation is unlikely to occur during cell pressure bonding and subsequent handling. Another object of the present invention is to provide a substrate for a liquid crystal panel, which includes a columnar spacer having flexibility that can follow thermal contraction and expansion of liquid crystal, and which can form and maintain a cell gap accurately and uniformly.

A second object of the present invention is to provide a columnar spacer capable of maintaining the cell gap accurately and uniformly even when the display area of the liquid crystal display device is large or the cell gap is very narrow. It is an object of the present invention to provide a substrate for a liquid crystal panel that can cope with the expansion of cell size and the narrowing of cell gap.

A third object of the present invention is to form an accurate and uniform cell gap without causing plastic deformation when used in a room temperature cell pressure bonding method (particularly when performing room temperature cell pressure bonding in the ODF method). An object of the present invention is to provide a substrate for a liquid crystal panel having a columnar spacer.

A fourth object of the present invention is to provide a liquid crystal panel excellent in display quality using the liquid crystal panel substrate according to the present invention.

A fifth object of the present invention is that the elastic deformation rate at room temperature is excellent, and in particular, the liquid crystal panel has sufficient hardness such that it is not plastically deformed at the time of cell pressure bonding and the subsequent handling, and the heat of the liquid crystal is high. It is intended to provide a photosensitive resin composition for forming a pattern, which can form a columnar spacer having flexibility that can follow constant contraction and expansion.

[0023]

A liquid crystal panel substrate according to the present invention is provided with a plurality of columnar spacers in a non-display area on the substrate, and the columnar spacers withstand a compressive load of 2.0 GPa at room temperature. The elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] is 60% or more.

The columnar spacers have sufficient hardness to prevent plastic deformation under a compressive load at room temperature, and flexibility to follow the contraction and expansion of the liquid crystal within the temperature range of the operating environment of the liquid crystal display device. .

Therefore, when the liquid crystal panel substrate according to the present invention and the mating substrate are bonded together by the room temperature cell pressure bonding method, the pressure unevenness is alleviated or absorbed so that the load is made uniform over the entire substrate to eliminate the gap unevenness. After the compression load is released, it can be almost completely restored to the original height and the cell gap can be maintained at a predetermined distance.

Further, in the completed liquid crystal panel, even if the external force such as impact or pressing force is temporarily applied, the cell gap is restored to the original state, so that the display unevenness can be prevented. Furthermore, since it is possible to follow the thermal contraction or expansion of the liquid crystal in a wide temperature range including room temperature, it is possible to prevent the generation of bubbles.

Further, the columnar spacer of the liquid crystal panel substrate according to the present invention has a very good restoring property even when it is deformed by a compressive load. Therefore, the liquid crystal panel substrate according to the present invention can accurately and uniformly maintain the cell gap even when the liquid crystal display device has a large display area or a very narrow cell gap.

The columnar spacer of the liquid crystal panel substrate according to the present invention exhibits appropriate elastic deformation at room temperature. Therefore, the liquid crystal panel substrate according to the present invention does not cause plastic deformation when the bonding is performed by the room temperature cell pressure bonding method,
An accurate and uniform cell gap can be formed. The columnar spacer of the liquid crystal panel substrate according to the present invention can be preferably used even when room temperature cell pressure bonding is performed in the ODF method.

In the liquid crystal panel substrate according to the present invention, the columnar spacer is provided in the non-display area on the substrate,
It is preferably used as a color filter having a pixel portion in the display area.

Next, a liquid crystal panel according to the present invention is a liquid crystal panel in which a display side substrate and a liquid crystal drive side substrate are opposed to each other, and liquid crystal is sealed between them, and the display side substrate and the liquid crystal drive At least one of the side substrates is a liquid crystal panel substrate according to the present invention.

The liquid crystal panel according to the present invention can maintain the cell gap accurately and evenly during cell pressure bonding and subsequent handling, so that it does not cause display unevenness and is excellent in image quality.

Next, the photocurable resin composition for pattern formation according to the present invention contains at least a polyfunctional acrylate monomer, a polymer and a photopolymerization initiator, and the content of the polyfunctional acrylate monomer is 50% by weight. The photocurable resin composition as described above, which has an elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] of 60% or more at room temperature after curing with a compressive load of 2.0 GPa. Characterize.

The photocurable resin composition according to the present invention is an acrylic curable resin containing a polyfunctional acrylate monomer in a high proportion of 50 to 80% by weight, and has a large elastic deformation rate and a small plastic deformation rate at room temperature. Indicates. This photocurable resin composition can be used as a material for forming a pattern, and can be particularly preferably used for forming a columnar spacer of the above liquid crystal panel.

At least a part of the polyfunctional acrylate monomer in the photocurable resin composition according to the present invention is an acidic polyfunctional acrylate monomer having one or more acidic groups and three or more ethylenically unsaturated bonds. In this case, the elastic deformation rate at room temperature is excellent, and in particular, sufficient hardness that plastic deformation is unlikely to occur during cell pressure bonding of the liquid crystal panel or during subsequent handling, and suppleness capable of following thermal contraction and expansion of the liquid crystal. In addition to being able to form a columnar spacer having a large thickness, the edge shape of the columnar spacer formed is good, and the columnar spacer has a ratio (S2 / S1) of the upper surface area (S2) to the lower surface area (S1) of 1 or less. In addition, a favorable forward tapered shape of 0.3 or more is likely to be formed, which is preferable.

[0035]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below with reference to the drawings. Note that, even in drawings showing different embodiments or conventional techniques, common reference numerals are used for corresponding details even if compositions, structures, shapes, physical properties and the like are different.

The liquid crystal panel substrate provided by the present invention is provided with a plurality of columnar spacers in the non-display area on the substrate, and the columnar spacers are 2.0 G at room temperature.
It is characterized in that the elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] is 60% or more with respect to a compressive load of Pa.

FIG. 3 shows an example of a color filter (color filter 10) belonging to the liquid crystal panel substrate according to the present invention.
3 is a plan view showing 3), and FIG. 4 is a vertical cross-sectional view of the same color filter 103 taken along the line AA.

The color filter 103 includes a black matrix 6 formed in a predetermined pattern on the transparent substrate 5, a pixel portion 7 (7R, 7G, 7B) formed in a predetermined pattern on the black matrix, and the pixel. The protective film 8 is formed so as to cover the portion. A transparent electrode 9 for driving a liquid crystal may be formed on the protective film, if necessary. An alignment film 10 is formed on the innermost surface of the color filter 103, which is a transparent electrode in this case.

The columnar spacers 12 are aligned with the area (non-display area) where the black matrix layer 6 is formed.
The transparent electrode 9 is formed at a plurality of predetermined locations (5 locations in FIG. 3). The columnar spacer 12 is formed on the transparent electrode 9, the pixel portion 7, or the protective film 8. In the color filter 101, the columnar spacers are formed in a sea-island shape on the protective film 8 via the transparent electrode 9, but the protective film 8 and the columnar spacers 12 are integrally formed,
You may form the layer of a transparent electrode so that it may be covered. When the color filter does not include the black matrix layer, columnar spacers can be formed in the area where the pixel portion is not formed.

As the transparent substrate 5 of the color filter 101, quartz glass, Pyrex (registered trademark) glass,
An inflexible transparent rigid material such as a synthetic quartz plate, or a transparent transparent flexible material such as a transparent resin film or an optical resin plate can be used. Among them, Corning's 1737 glass is a material with a small coefficient of thermal expansion, has excellent dimensional stability and workability in high-temperature heat treatment, and is a non-alkali glass that does not contain an alkali component in the glass. It is suitable as a color filter for color liquid crystal display devices of the matrix type.

The black matrix layer 6 is provided in the pixel portions 7R, 7G, in order to improve the contrast of the display image.
It is provided so as to surround the space between 7B and the outside of the pixel portion formation region. As a method for forming the black matrix layer 6, there are a method using a photosensitive resist and a method using a photocurable resin composition containing light-shielding particles.

In the method using a photosensitive resist,
First, a metal thin film such as chromium is formed as a light shielding layer on the transparent substrate 5 by a vapor phase method such as a sputtering method or a vacuum deposition method, or a resin such as a polyimide resin, an acrylic resin or an epoxy resin is coated with carbon black or the like. A resin layer made of a resin composition containing the light-shielding particles is formed by a coating method such as a spin coater, a roll coater, spraying or printing. A known positive-type or negative-type photosensitive resist is applied on the light-shielding layer made of such a metal thin film or a light-shielding resin to form a photosensitive resist layer, which is exposed through a photomask for a black matrix. ,develop. Then, by etching the light-shielding layer in the portion exposed by the development and removing the remaining photosensitive resist,
The black matrix layer 6 can be formed.

In the method using the photocurable resin composition containing the light-shielding particles, first, the photocurable resin containing the light-shielding particles such as carbon black or metal oxide on the transparent substrate 5. By applying the composition, if necessary to dry to form a photosensitive coating film, the coating film is exposed through a photomask for a black matrix, developed, and subjected to heat treatment as necessary, The black matrix layer 6 can be formed. As the photocurable resin composition to be mixed with the light shielding particles, the photocurable resin composition used for forming the columnar spacer described later may be used as it is.

The thickness of the black matrix layer is about 1000 to 2000 Å for the metal thin film, and about 0.5 to 2.5 μm for the light shielding resin layer.

The pixel portion 7 is formed by arranging a red pattern, a green pattern, and a blue pattern in a desired form such as a mosaic type, a stripe type, a triangle type, and a four-pixel arrangement type to form a display area. The pixel portion can be formed by a known method such as a pigment dispersion method, a dyeing method, a printing method, or an electrodeposition method. Among them, a pigment using a photocurable resin composition containing a colorant such as a pigment is used. It is preferably formed by a dispersion method.

In the case of the pigment dispersion method, first, a colorant such as a pigment is dispersed in the photocurable resin composition to prepare a red colorant,
Photocurable colored resin compositions for green and blue are prepared respectively. Next, a certain color, for example, a photocurable red resin composition is applied onto the transparent substrate 5 by a known method such as spin coating so as to cover the black matrix layer 6, to form a photocurable red resin layer. Then, the red pixel portion 7R is formed by exposing through a red pattern photomask, alkali developing, and then heat curing in a clean oven or the like. Then, the green and blue photocurable colored resin compositions are sequentially used to similarly pattern each color to form the green pixel portion 7G and the blue pixel portion 7B.

As the colorant, there is heat resistance which can endure the heating process of the color filter among organic colorants and inorganic colorants in accordance with the required color of R, G, B, etc. of the pixel portion, and it is good. Fine particles that can be dispersed in can be selected and used.

As the organic colorant, for example, a dye, an organic pigment, a natural pigment or the like can be used. Further, as the inorganic colorant, for example, an inorganic pigment, an extender pigment or the like can be used.

Specific examples of the organic pigment include color index (CI; The Society of Dyers and Colorists).
(Published by the company), compounds that are classified as Pigment, that is, those that have the following color index (CI) numbers are listed. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 138, CI Pigment Yellow 150, CI Pigment Yellow 18
0, yellow pigments such as CI Pigment Yellow 185; red pigments such as CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 254, CI Pigment Red 177; and CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4,
CI pigment blue 15: 6 and other blue pigments; CI pigment violet 23:19; CI pigment green 36.

Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), and cadmium red. , Ultramarine, dark blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. In the present invention, the colorant may be used alone or in combination of two or more kinds.

As the photocurable resin composition to be mixed with the colorant, the photocurable resin composition used for forming the columnar spacer described later may be used as it is.

The thickness of the pixel portion is usually 0.5 to 2.5 μm.
The degree. Further, even if the thickness of the pixel portion of each color is changed such that the red pixel portion 7R is the thinnest, the green pixel portion 7G and the blue pixel portion 7B are thicker in this order, the optimum liquid crystal layer thickness is set for each color. Good.

The protective film 8 is provided to flatten the surface of the color filter and prevent the components contained in the pixel portion 7 from eluting into the liquid crystal layer. The protective film 8 is
A known negative-type photocurable transparent resin composition or thermosetting transparent resin composition is applied by a method such as spin coater, roll coater, spraying or printing so as to cover the black matrix layer 6 and the pixel portion 7. It can be formed by curing with light or heat. As the photocurable transparent resin composition, the photocurable resin composition used for forming a columnar spacer described later may be used as it is.

The thickness of the protective film depends on the light transmittance of the resin composition,
It is set in consideration of the surface condition of the color filter, and is, for example, about 0.1 to 2.0 μm. When a spin coater is used, the rotation speed is set within the range of 500 to 1500 rotations / minute.

The transparent electrode film 9 on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (S).
nO), etc., and their alloys, etc. are formed by a general method such as a sputtering method, a vacuum deposition method, a CVD method, etc., and if necessary, by etching using a photoresist or using a jig, It is a pattern. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.

A plurality of columnar spacers 12 are provided in a non-display area on the substrate in order to maintain a cell gap when the color filter 103 is bonded to a liquid crystal driving side substrate such as a TFT array substrate. The columnar spacer 12 is 2
It has a certain height in the range of about 10 μm,
The protrusion height can be appropriately set based on the thickness required for the liquid crystal layer and the like. Further, the thickness of the columnar spacer 12 is 5 to
It can be appropriately set within a range of about 20 μm. Further, the formation density (density) of the columnar spacers 12 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape of the columnar spacers, the material, and the like. One per one set of each pixel develops a necessary and sufficient spacer function. The shape of such a columnar spacer may be any columnar shape, and may be, for example, a columnar shape, a prismatic shape, a truncated cone shape, or the like.

In the liquid crystal panel substrate according to the present invention represented by the color filter 103, the columnar spacer has an elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] against a compressive load of 2.0 GPa at room temperature. Is over 60%,
It is preferably 70% or more, particularly preferably 80% or more.

In the present invention, "room temperature" means the environmental temperature encountered in daily life, and its range is not clear,
It includes a temperature range of at least 1 ° C to 35 ° C.

The elastic deformation rate of the columnar spacer can be measured by the following method. As a device that measures the amount of deformation by applying a load to the columnar spacer,
A Fisherscope H-100 (manufactured by Fisher Instruments Co., Ltd.) (using an indenter having a flat surface of 100 μm × 100 μm obtained by polishing the head of a Vickers indenter (quadrangular pyramid shape)) can be used. FIG. 3 shows the behavior of the columnar spacer in the process of compressing the columnar spacer having the height T and releasing the load by using such a device, and the total deformation amount (T1), the plastic deformation amount (T2) and the elastic deformation. Amount (T
3) It shows the mutual relationship. First, the color filter 103 or another substrate for a liquid crystal panel according to the present invention is placed at room temperature, and an indenter is brought into contact with the upper bottom portion of the columnar spacer using the above-mentioned device to push the columnar spacer in the height direction of the columnar spacer. 22m toward (in the thickness direction of the film)
The load is increased while increasing the load at a rate of Pa / sec. When the compressive load reaches 2.0 GPa, it is held for 5 seconds and the total deformation amount (T1) of the columnar spacer is measured. Next, by raising the indenter pressed against the columnar spacer,
The load is removed at a rate of 2 mPa / sec, and the compression load is 0.
The amount of deformation remaining when returning to (zero), that is, the amount of plastic deformation (T2) is measured. Then, the plastic deformation amount (T2) is subtracted from the total deformation amount (T1) to calculate the deformation amount immediately restored by releasing the load, that is, the elastic deformation amount (T3). The values of the total deformation amount (T1) and the elastic deformation amount (T3) thus obtained are calculated by the following equation: (elastic deformation amount (T
3) / total deformation amount (T1)) × 100 to obtain the elastic deformation rate (%).

The elastic deformation rate of the columnar spacer at room temperature is 6
If it is less than 0%, it tends to be plastically deformed at room temperature,
The spacer function of maintaining an accurate and uniform cell gap cannot be fulfilled. In this case, for example, when assembling the color filter and the liquid crystal driving side substrate by the room temperature cell pressure bonding method, pressure unevenness cannot be alleviated or absorbed and gap unevenness is likely to occur, or the assembled liquid crystal panel is subject to impact or pressing. When an external force such as a pressure is applied, it tends to be distorted and cannot be returned to the original state, or it is difficult to follow thermal contraction or expansion of the liquid crystal in a wide temperature range including room temperature, which causes bubbles.

In the present invention, the columnar spacers have an elastic deformation rate of 60% or more under a compressive load of 2.0 GPa at room temperature, and a total deformation rate [= (total deformation amount (T1) / height (T ) × 100)] is preferably 80% or less. If the total deformation rate is higher than 80%, the color filter and the liquid crystal drive substrate may come into contact with each other during cell pressure bonding, damaging the color filter or the liquid crystal drive substrate.
As a result, display unevenness may occur.

The columnar spacer satisfying the above physical properties is
It can be formed using a photocurable resin composition. As the photocurable resin composition, a composition containing at least a polyfunctional acrylate monomer, a polymer and a photopolymerization initiator is preferably used.

As the polyfunctional acrylate monomer compounded in the photocurable resin composition, a compound having two or more ethylenically unsaturated bond-containing groups such as an acrylic group and a methacrylic group is used, and specifically, ethylene glycol is used. (Meta)
Acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, 1,4-butanediol diacrylate, pentaerythritol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( Examples thereof include (meth) acrylate.

The polyfunctional acrylate monomer may be used in combination of two or more kinds. In the present invention, (meth) acrylic means either acrylic or methacrylic, and (meth) acrylate means either an acrylate group or a methacrylate.

In the present invention, the content of such a polyfunctional acrylate monomer is preferably 50% by weight or more based on the total solid content of the photocurable resin composition. Here, the total solid content is the total amount of all components other than the solvent, and also includes a liquid monomer component. When the content of the polyfunctional acrylate monomer in the photocurable resin composition is less than 50% by weight, the elastic deformation rate of the pattern formed by exposing and developing using the photocurable resin composition becomes small. ,
It becomes difficult to form a pattern having a large elastic deformation rate and a small plastic deformation rate in a wide temperature range. Here, the elastic deformation rate is calculated by the above equation, and the plastic deformation rate (%) is calculated by the following equation: [(Plastic deformation amount (T2) / Total deformation amount (T
1)) × 100].

The above polyfunctional acrylate monomer is 3
It is preferable to include a monomer having a functional or higher ethylenically unsaturated bond, and the content thereof preferably accounts for about 30 to 95% by weight of the amount of the polyfunctional acrylate monomer used.

By increasing the content of the polyfunctional acrylate monomer in the photocurable resin composition, as described above, it is possible to form a cured pattern having a large elastic deformation rate and a small plastic deformation rate in a wide temperature range. However, on the other hand, it becomes difficult to obtain good developability, the precision of the pattern edge shape is lowered, or the forward tapered shape preferable for the columnar spacer (that is, the upper surface area (S2) and the lower surface area (S1) of the columnar spacer). Such as a trapezoid having a ratio of 1 or less) is likely to occur. The reason is that when a large amount of a polyfunctional acrylate monomer is added to the photocurable resin composition, the crosslinking density after curing becomes extremely high, which contributes to making elastic deformation superior to plastic deformation. It is presumed that the solubility of the compound is too low, which is disadvantageous in obtaining good developability.

In order to solve such inconvenience, 3
Among polyfunctional or higher functional acrylate monomers, those having one or more acidic groups and three or more ethylenic unsaturated bonds in one molecule (hereinafter, referred to as "trifunctional or higher functional polyfunctional acrylate monomer") Is preferably used.

The trifunctional or higher functional polyfunctional acidic acrylate monomer has a role of improving the crosslink density of the resin composition and a role of improving the alkali developability. Therefore, when the columnar spacer is formed using the resin composition containing the acidic polyfunctional acrylate monomer, the edge shape of the columnar spacer becomes good, and the upper surface area (S2) and the lower surface area (S1) of the columnar spacer are improved. The ratio (S2 / S1) to 1) is 1 or less and 0.3 or more, and a good forward tapered shape is easily formed. Furthermore, the elastic deformation rate at room temperature is excellent, and in particular, sufficient hardness that plastic deformation is unlikely to occur during cell pressure bonding of the liquid crystal panel or during subsequent handling, and flexibility that can follow thermal contraction and expansion of the liquid crystal. A columnar spacer having can be formed.

The acidic group of the acidic polyfunctional acrylate monomer may be any one capable of alkali development, and examples thereof include a carboxyl group, a sulfonic acid group and a phosphoric acid group. A carboxyl group is preferred from the standpoint of sex.

Examples of the trifunctional or higher functional polyfunctional acid acrylate monomer as described above include (1) a polyfunctional (meth) having a carboxyl group introduced by modifying a hydroxyl group-containing polyfunctional (meth) acrylate with a dibasic acid anhydride. ) Acrylate, or (2) polyfunctional (meth) acrylate in which a sulfonic acid group is introduced by modifying aromatic polyfunctional (meth) acrylate with concentrated sulfuric acid or fuming sulfuric acid can be used.

As the trifunctional or higher functional polyfunctional acidic acrylate monomer, those represented by the following general formulas (1) and (2) are preferable.

[0073]

[Chemical 1]

(In the formula (1), n is 0 to 14 and m is 1 to 8. In the formula (2), R is the same as in the formula (1) and n is 0 to 14). , P is 1 to 8, and q is 1 to
8 A plurality of R, T, and G present in one molecule may be the same or different. The specific examples of the acidic polyfunctional acrylate monomer represented by the formulas (1) and (2) include TO, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd.
-756, and TO-1382 which is a carboxyl group-containing pentafunctional acrylate.

As the polymer compounded in the photocurable resin composition, ethylene-vinyl acetate copolymer, ethylene-
Vinyl chloride copolymer, ethylene-vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, AB
S resin, polymethacrylic acid resin, ethylene-methacrylic acid resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, Polybutylene terephthalate, polycarbonate,
Polyvinyl acetal, polyether ether ketone,
Examples thereof include polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamideimide resin, polyamic acid resin, opolyetherimide resin, phenol resin, urea resin and the like.

Further, as the polymer, a polymerizable monomer such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, sec-butyl (meth) acrylate and isobutyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) Acrylate, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, glycidyl (meth)
One or more selected from acrylates, (meth) acrylic acid, a dimer of acrylic acid (for example, M-5600 manufactured by Toagosei Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, A polymer or copolymer composed of one or more kinds selected from vinyl acetic acid and these anhydrides can also be exemplified. Moreover, the polymer etc. which added the ethylenically unsaturated compound which has a glycidyl group or a hydroxyl group to the said copolymer can also be illustrated, but it is not limited to these.

Among the above-exemplified polymers, a polymer containing an ethylenically unsaturated bond forms a cross-linking bond with a monomer, and an excellent strength can be obtained, so that it is particularly preferably used.

The content of such a polymer is preferably 10 to 40% by weight based on the total solid content of the photocurable resin composition.

The photopolymerization initiator to be added to the photocurable resin composition may be ultraviolet light, ionizing radiation, visible light, or
A photo-radical polymerization initiator that can be activated at other wavelengths, particularly at an energy ray of 365 nm or less, can be used. Specific examples of such a photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-aminoacetophenone, 4,4-Dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpro Piophenone, p
-Tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethyl acetal, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-
tert-Butylanthraquinone, 2-amylanthraquinone, β-chloranthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-
Bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2-
(O-Methoxycarbonyl) oxime, 1-phenyl-
Propanedion-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2-
(O-Ethoxycarbonyl) oxime, 1-phenyl-
3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1 [4-
(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, ADEKA Corporation N1717, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide,
Examples thereof include a combination of a photoreducing dye such as eosin and methylene blue with a reducing agent such as ascorbic acid and triethanolamine. In the present invention, these photopolymerization initiators may be used alone or in combination of two or more.

The content of such a photopolymerization initiator is preferably 2 to 20% by weight based on the total solid content of the photocurable resin composition.

The photocurable resin composition may optionally contain components other than the polyfunctional acrylate monomer, the polymer and the photopolymerization initiator. For example, an epoxy resin may be added to the photocurable resin composition for the purpose of improving heat resistance, adhesion and chemical resistance (particularly alkali resistance). Examples of epoxy resins that can be used include Epicort series, trade name, manufactured by Mitsubishi Petrochemical Shell Co., Ltd., Celoxide series, trade name, manufactured by Daicel Corporation, and Epolide series, trade name, manufactured by the same company. .
Examples of the epoxy resin further include bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, novolac type epoxy resin, polycarboxylic acid glycidyl ester, polyol glycidyl ester, aliphatic or alicyclic epoxy resin. Examples thereof include resins, amine epoxy resins, triphenol methane type epoxy resins, dihydroxybenzene type epoxy resins, and copolymerized epoxy compounds of glycidyl (meth) acrylate and a radically polymerizable monomer. In the present invention, these epoxy resins may be used alone or in combination of two or more.

The content of such an epoxy resin is preferably 0 to 10% by weight based on the total solid content of the photocurable resin composition.

Solid components are dissolved in the photocurable resin composition,
In order to disperse and adjust the coating suitability for spin coating and the like, a solvent is usually added. As the solvent, it is preferable to use a solvent having a relatively high boiling point so as to have good solubility or dispersibility in a compounding component such as a monomer, a polymer, a photopolymerization initiator and the like, and a good spin coating property.

Examples of usable solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone and N-. Ketones such as methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether,
Glycol ethers such as dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether;
Examples of acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. be able to.

From these solvents, only one kind or a mixture of two or more kinds is used, and the solid content concentration is usually adjusted to 5 to 50% by weight.

To prepare the curable resin composition, a polyfunctional acrylate monomer, a polymer, a photopolymerization initiator and, if necessary, other components are added to a suitable solvent, and a paint shaker, a bead mill, a sand grind are added. mill,
It may be dissolved and dispersed by a general method such as a ball mill, an attritor mill, a two roll mill, or a three roll mill.

In order to form the columnar spacers, first, the coating liquid of the photocurable resin composition is directly applied onto the transparent substrate by a method such as spin coater, roll coater, spraying, printing, or other method such as a transparent electrode. To form a photocurable resin layer. The rotation speed of the spin coater is 500 to 1500 as in the case of forming the protective film.
It may be set within the range of rotation / minute. Next, this resin layer is exposed through a photomask for a columnar spacer, developed with a developing solution such as an alkaline solution to form a columnar pattern, and this columnar pattern is heat-treated in a clean oven or the like if necessary ( By post-baking), columnar spacers are formed. The columnar spacer can be provided directly on the color filter or indirectly via another layer. For example, a transparent electrode such as ITO or a protective film may be formed on a color filter, and a columnar spacer may be formed on the transparent electrode, or a protective film and a transparent electrode may be formed on the color filter in this order, and further on the transparent electrode. A columnar sparser may be formed on.

The alignment film 10 is provided on the inner surface side of the color filter so as to cover the display portion including the pixel portion 7 and the non-display portion including the black matrix layer 6 and the columnar spacer 12. The alignment film is formed by applying a coating solution containing a resin such as a polyimide resin by a known method such as spin coating,
It can be formed by drying, and if necessary, curing with heat or light, and then rubbing.

When the color filter 103 (display side substrate) thus obtained and the TFT array substrate (liquid crystal drive side substrate) are opposed to each other and the inner peripheral edge portions of both substrates are joined with a sealant, both substrates are They are bonded together while maintaining a cell gap of a predetermined distance. Then, the gap between the substrates is filled with liquid crystal and hermetically sealed, whereby an active matrix type color liquid crystal display device belonging to the liquid crystal panel according to the present invention can be obtained.

In order to bond the liquid crystal panel substrate according to the present invention represented by the color filter 103 to the mating substrate, it is preferable to apply the room temperature cell pressure bonding method. In the conventional cell assembling process of a liquid crystal panel, first, a thermosetting agent such as an epoxy curing agent is used to form a color filter substrate on an array substrate on which spacer beads are dispersed, or an array on a color filter substrate on which spacer beads are dispersed. It is common practice to press-bond the substrates at a high temperature and then inject a liquid crystal between the substrates in a vacuum to seal the substrates. However, in such a method, the number of panel assembling steps is large, so that the manufacturing speed and the yield are likely to be lowered. In addition, in the case of a medium- or small-sized liquid crystal panel, the number of pixels is small, so that the driving capacity is small. Therefore, it is sufficient to mount the driving driver on the three sides of the panel, and the liquid crystal can be injected from the remaining one side. Therefore, in the case of a high-definition large-sized liquid crystal panel, the number of pixels increases, and a large drive capacity is required. Therefore, a driver mounting area is required on the four sides of the panel, and if the driver mounting area touches the liquid crystal when injecting the liquid crystal, the reliability is likely to decrease due to contamination of the liquid crystal.

In the ODF method, after dropping liquid crystal on the substrate,
This is a method of pasting opposite substrates at a time with a predetermined cell gap left open, because problems such as nonuniform cell gap due to spacer beads, insufficient adhesive strength of sealing material, and liquid crystal contamination have been problems in the past. It has been difficult to industrially apply it to industry, but in recent years, industrial production has been carried out in view of the situation such as the development of columnar spacers, improvement of their reliability, and the development of photo-curing sealant with good adhesiveness. The application of has come to be expected. Since the columnar spacer provided by the present invention has an excellent elastic deformation rate at room temperature and a high cell gap accuracy, it can be suitably used even when performing room temperature cell pressure bonding by such an ODF method.

Since the liquid crystal panel substrate according to the present invention is provided with the columnar spacers that are elastically deformed appropriately under a compressive load at room temperature, pressure unevenness may occur when bonding is performed by the room temperature cell pressure bonding method. By relaxing or absorbing, the load is made uniform over the entire substrate to prevent the occurrence of gap unevenness, and after releasing the compressive load, the cell gap can be maintained at a predetermined distance by almost completely restoring the original height.

Further, in the completed liquid crystal panel, even if the external force such as impact or pressing force is applied to the liquid crystal panel, the cell gap is restored to the original state even if the liquid crystal panel is temporarily damaged, so that display unevenness can be prevented. Furthermore, since it is possible to follow the thermal contraction or expansion of the liquid crystal in a wide temperature range including room temperature, it is possible to prevent the generation of bubbles.

Therefore, the liquid crystal panel according to the present invention hardly causes display unevenness and is excellent in image quality.

Although the liquid crystal panel substrate of the present invention has been described above by taking the color filter as an example, the present invention can be applied to the display side substrate other than the color filter such as a monochrome color filter, and the TFT array. It can also be applied to a liquid crystal driving side substrate such as a substrate or a simple matrix driving substrate. When applied to a liquid crystal driving side substrate such as a TFT array substrate, the columnar spacers on the liquid crystal driving side substrate are provided in a region (non-display region) overlapping the black matrix layer of the display side substrate to be combined.

[0096]

EXAMPLES Preparation Example 1 (1) Synthesis of Copolymer Resin Solution 1 63 parts by weight of methyl methacrylate (MMA), 12 parts by weight of acrylic acid (AA), methacrylic acid-
After charging 6 parts by weight of 2-hydroxyethyl (HEMA) and 88 parts by weight of diethylene glycol dimethyl ether (DMDG) and stirring and dissolving them, 7 parts by weight of 2,2′-azobis (2-methylbutyronitrile) was added. , Homogeneously dissolved. Then, the mixture was stirred at 85 ° C. for 2 hours under a nitrogen stream and further reacted at 100 ° C. for 1 hour. Glycidyl methacrylate (GMA) was further added to the obtained solution.
Parts by weight, 0.4 parts by weight of triethylamine, and 0.2 parts by weight of hydroquinone were added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a target copolymer resin solution 1 (solid content 50%). The physical properties of the resulting copolymer are shown in Table 1.

[0097]

[Table 1]

(2) Preparation of curable resin composition 1 The following amount of each material: Copolymer resin solution 1 (solid content 50%): 16 parts by weight Dipentaerythritol pentaacrylate (SR399, Sartomer Co.): 24 Parts by weight Orthocresol novolac type epoxy resin (Epicoat 180S70, manufactured by Yuka Shell Epoxy Co., Ltd.): 4 parts by weight 2-methyl-1- (4-methylthiophenyl) -2-
Morpholinopropan-1-one (4 parts by weight) and diethylene glycol dimethyl ether (52 parts by weight) were stirred and mixed at room temperature to obtain a curable resin composition 1.

(3) Preparation of curable resin composition 2 The following amount of each material: Copolymer resin solution 1 (solid content 50%): 32 parts by weight Dipentaerythritol pentaacrylate (SR399, Sartomer Co.): 16 Parts by weight Orthocresol novolac type epoxy resin (Epicoat 180S70, manufactured by Yuka Shell Epoxy Co., Ltd.): 4 parts by weight 2-methyl-1- (4-methylthiophenyl) -2-
Morpholinopropan-1-one: 4 parts by weight / diethylene glycol dimethyl ether: 44 parts by weight were stirred and mixed at room temperature to obtain a curable resin composition 2.

(4) Preparation of curable resin composition 3 The following amount of each material: Copolymer resin solution 1 (solid content 50%): 8 parts by weight, carboxyl group-containing pentafunctional acrylate monomer (Toagosei Co., Ltd.) Manufactured by TO-1382): 32 parts by weight orthocresol novolac type epoxy resin (Epicoat 180S70 manufactured by Yuka Shell Epoxy Co., Ltd.): 2 parts by weight 2-methyl-1- (4-methylthiophenyl) -2-
Morpholinopropan-1-one: 2 parts by weight / diethylene glycol dimethyl ether: 56 parts by weight were stirred and mixed at room temperature to obtain a curable resin composition 3.

(Example 1) (1) Formation of black matrix First, the following amount: Black pigment: 23 parts Polymer dispersant (manufactured by BYK Japan KK)
sperbyk 111): 2 parts by weight Solvent (diethylene glycol dimethyl ether): 7
5 parts by weight of the components were mixed and sufficiently dispersed by a sand mill to prepare a black pigment dispersion liquid.

Next, the following amount -The above black pigment dispersion: 61 parts by weight -Curable resin composition 1: 20 parts by weight ・ Diethylene glycol dimethyl ether: 30 parts by weight The components described in (1) above were thoroughly mixed to obtain a light-shielding layer composition.

Then, the above composition for a light-shielding layer was applied onto a glass substrate (AL material manufactured by Asahi Glass Co., Ltd.) having a thickness of 1.1 mm by a spin coater and dried at 100 ° C. for 3 minutes to form a light-shielding film having a thickness of about 1 μm. Layers were formed. The light-shielding layer is exposed to a light-shielding pattern with an ultra-high pressure mercury lamp, developed with a 0.05% potassium hydroxide aqueous solution, and then subjected to heat treatment by leaving the substrate in an atmosphere of 180 ° C. for 30 minutes. A black matrix was formed in the area where the light-shielding portion should be formed.

(2) Formation of Colored Layer A red curable resin composition having the following composition was applied by a spin coating method (coating thickness: 1.5 μm) on the substrate on which the black matrix was formed as described above, and then, It was dried in an oven at 70 ° C. for 30 minutes.

Then, a photomask was placed at a distance of 100 μm from the coating film of the red curable resin composition, and a 2.0 kW ultrahigh pressure mercury lamp was used by a proximity liner to form only a region corresponding to the formation region of the colored layer. The sample was exposed to ultraviolet rays for 10 seconds. Then, it was immersed in a 0.05 wt% potassium hydroxide aqueous solution (liquid temperature 23 ° C.) for 1 minute for alkali development to remove only the uncured portion of the coating film of the red curable resin composition. Then, the substrate is placed in an atmosphere of 180 ° C. for 3
By leaving it for 0 minutes, heat treatment was performed to form a red relief pattern in the region where the red pixel was to be formed.

Next, using the green curable resin composition having the following composition, in the same process as the formation of the red relief pattern,
A green relief pattern was formed in a region where a green pixel should be formed.

Further, a blue curable resin composition having the following composition was used to form a blue relief pattern in a region where a blue pixel is to be formed, by the same steps as the formation of a red relief pattern, and red (R), A colored layer composed of three colors of green (G) and blue (B) was formed.

A. Composition of red curable resin composition C.I. I. Pigment Red 177: 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, curable resin composition 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight b. Composition of green curable resin composition C.I. I. Pigment Green 36:10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, curable resin composition 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight c. Composition of blue curable resin composition C.I. I. Pigment Blue 15: 6: 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, curable resin composition 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight (3) Formation of protective film The curable resin composition 1 was applied onto the substrate having the colored layer formed as described above by a spin coating method and dried to form a coating film having a dry film thickness of 2 μm.

100 μm from the coating film of the curable resin composition 1
A photomask was placed at a distance of m, and an ultraviolet ray was irradiated for 10 seconds only by a proximity liner using a 2.0 kW ultra-high pressure mercury lamp on an area corresponding to the area where the colored layer was formed. Next, it was immersed in a 0.05 wt% aqueous solution of potassium hydroxide (liquid temperature: 23 ° C.) for 1 minute for alkali development to remove only the uncured portion of the coating film of the curable resin composition.
Then, the substrate was left in an atmosphere of 200 ° C. for 30 minutes for heat treatment to form a protective film, and a color filter of the present invention was obtained.

(4) Formation of Spacer The curable resin composition 1 was applied onto the substrate having the colored layer formed as described above by the spin coating method and dried to form a coating film having a dry film thickness of 5 μm.

100 μm from the coating film of the curable resin composition 1
A photomask was placed at a distance of m, and a 2.0 kW ultra-high pressure mercury lamp was used by a proximity liner to irradiate only the spacer formation region on the black matrix with ultraviolet rays for 10 seconds. Next, it was immersed in a 0.05 wt% aqueous solution of potassium hydroxide (liquid temperature: 23 ° C.) for 1 minute for alkali development to remove only the uncured portion of the coating film of the curable resin composition. Then, the substrate was left in an atmosphere of 200 ° C. for 30 minutes for heat treatment to form a fixed spacer having an upper end area of 100 μm ² and a height T of 4.5 μm to obtain a color filter of the present invention. .

(5) Fabrication of Liquid Crystal Display Device On the surface of the color filter obtained as described above including the fixed spacers, argon and oxygen were used as discharge gases at a substrate temperature of 200 ° C., and ITO was targeted by a DC magnetron sputtering method. As a transparent electrode film was formed. After that, an alignment film made of polyimide was further formed on the transparent electrode film.

Then, a required amount of TN liquid crystal was dropped on the glass substrate on which the TFT was formed, the above color filters were superposed, and a UV curable resin was used as a sealant, and a pressure of 0.3 kg / cm ² was applied at room temperature. While 400 mJ / c
The liquid crystal display device of the present invention was manufactured by exposing the cells at an irradiation dose of m ² to bond and assemble the cells.

Example 2 (1) Formation of Spacer A color filter of Example 2 was obtained in the same manner as in Example 1 except that the fixed spacer was formed using the curable resin composition 3.

(2) Production of Liquid Crystal Display Device A liquid crystal display device of Example 2 was produced in the same manner as in Example 1 except that the color filter of Example 2 obtained as described above was used.

Comparative Example 1 (1) Formation of Spacer A color filter of Comparative Example 1 was obtained in the same manner as in Example 1 except that the fixed spacer was formed using the curable resin composition 2.

(2) Production of Liquid Crystal Display Device A liquid crystal display device of Comparative Example 1 was produced in the same manner as in Example 1 except that the color filter of Comparative Example 1 obtained as described above was used.

(Evaluation of developability) The developability of the fixed spacers of the color filters obtained in Examples 1 and 2 and Comparative Example 1 was evaluated from the development time. Moreover, the upper surface area (S2) and the lower surface area (S1) of the obtained spacer were calculated from the SEM photograph, and the taper shape (S2 / S1) was evaluated. The results are shown in Table 2.

[0119]

[Table 2]

(Evaluation of Elastic Deformation Rate) The fixed spacers of the color filters obtained in Examples 1 and 2 and Comparative Example 1 were polished with a Vickers indenter (quadrangular pyramid shape) to 100.
22M in the thickness direction at room temperature using a Fisher Instruments H-100 manufactured by Fischer Instruments Co., Ltd. equipped with an indenter having a flat surface of μm × 100 μm.
After applying a load up to 2 GPa at a rate of Pa / sec and holding for 5 seconds, the deformation amount (μm) when the load is removed at a rate of 22 MPa / sec in the thickness direction is measured, and the total deformation amount T1,
The amount of plastic deformation T2 and the amount of elastic deformation T3 were obtained, and the elastic deformation rate [(T3 / T1) × 100] was calculated. The results are shown in Table 3.

(Evaluation of Liquid Crystal Display) Using the liquid crystal display devices obtained in Examples 1 and 2 and Comparative Example 1, the presence or absence of color unevenness due to the difference in fixed spacers was visually observed. The results are shown in Table 3.

[0122]

[Table 3]

[0123]

As described above, the liquid crystal panel substrate according to the present invention has an elastic deformation rate [(elastic deformation amount / total deformation amount) × 10 at room temperature against a compressive load of 2.0 GPa.
0] is 60% or more.

The columnar spacers provided on the liquid crystal panel substrate according to the present invention have sufficient hardness so that they are not plastically deformed by a compressive load at room temperature, and the liquid crystal shrinks and expands within the operating environment temperature range of the liquid crystal display device. It has the flexibility to follow.

Therefore, when the liquid crystal panel substrate according to the present invention and the mating substrate are bonded together by the room temperature cell pressure bonding method, the uneven pressure is alleviated or absorbed so that the load is made uniform over the entire substrate to prevent the uneven gap. After the compression load is released, it can be almost completely restored to the original height and the cell gap can be maintained at a predetermined distance.

Further, in the completed liquid crystal panel, even if the external force such as impact or pressing force is temporarily applied, the cell gap is restored to the original state, so that the display unevenness can be prevented. Furthermore, since it is possible to follow the thermal contraction or expansion of the liquid crystal in a wide temperature range including room temperature, it is possible to prevent the generation of bubbles.

Further, the columnar spacer of the liquid crystal panel substrate according to the present invention has a very good restoring property even when it is deformed by a compressive load. Therefore, the liquid crystal panel substrate according to the present invention can accurately and uniformly maintain the cell gap even when the liquid crystal display device has a large display area or a very narrow cell gap.

Further, the columnar spacer of the liquid crystal panel substrate according to the present invention exhibits appropriate elastic deformation at room temperature. Therefore, the liquid crystal panel substrate according to the present invention does not cause plastic deformation when the bonding is performed by the room temperature cell pressure bonding method,
An accurate and uniform cell gap can be formed. The columnar spacer of the liquid crystal panel substrate according to the present invention can be preferably used even when room temperature cell pressure bonding is performed in the ODF method.

Further, in the liquid crystal panel according to the present invention, at least one of the display side substrate such as a color filter and the liquid crystal driving side substrate such as a TFT array substrate is the liquid crystal panel substrate according to the present invention.

Since the liquid crystal panel according to the present invention can maintain the cell gap accurately and uniformly during cell pressure bonding and subsequent handling, it is less likely to cause display unevenness and is excellent in image quality.

The photocurable resin composition according to the present invention is an acrylic curable resin containing a polyfunctional acrylate monomer in a high proportion of 50% by weight or more, and has a large elastic deformation rate and a small plastic deformation rate at room temperature. Show. This photocurable resin composition can be used as a material for forming a pattern, and can be particularly preferably used for forming a columnar spacer of the above liquid crystal panel.

When an acidic polyfunctional acrylate monomer having three or more functional groups is used as at least a part of the above polyfunctional acrylate monomer, the elastic deformation rate at room temperature is excellent,
In particular, it is possible to form a columnar spacer having sufficient hardness that is not easily plastically deformed during cell pressure bonding of the above-mentioned liquid crystal panel and subsequent handling, and suppleness that can follow thermal contraction and expansion of liquid crystal. The columnar spacer has a good edge shape, and the columnar spacer has a ratio (S2 / S1) of the upper surface area (S2) to the lower surface area (S1) of 1
It is very preferable since a favorable forward tapered shape of 0.3 or more is easily formed.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an example of a conventional liquid crystal panel.

FIG. 2 is a schematic cross-sectional view of another example of a conventional liquid crystal panel.

FIG. 3 is a plan view of an example of a liquid crystal panel substrate according to the present invention.

FIG. 4 is a cross-sectional view of an example of a liquid crystal panel substrate according to the present invention.

FIG. 5 is a diagram showing a relationship between a load and a deformation amount of a columnar spacer.

[Explanation of symbols]

1 ... Color filter 103 ... Color filter 2 ... TFT array substrate 3 ... Gap 4 ... Sealing material 5: Transparent substrate 6 ... Black matrix layer 7 (7R, 7G, 7B) ... Pixel part 8 ... Protective film 9 ... Transparent electrode film 10 ... Alignment film 11 ... Particle spacer 12 ... Column spacer

Continued front page    F term (reference) 2H025 AA00 AA03 AA18 AB13 AB14                       AC01 AD01 BC13 BJ07                 2H048 BA02 BA11 BA45 BA48 BB02                       BB08 BB14 BB15 BB37 BB44                 2H089 LA04 LA09 LA16 MA04X                       MA07X NA05 NA07 NA22                       NA24 NA32 PA05 PA06 QA04                       QA14 QA16 SA17 TA01 TA09                       TA12 TA13                 4J026 AA02 AA12 AA17 AA25 AA30                       AA34 AA38 AA43 AA45 AA48                       AA49 AA53 AA54 AA68 AB01                       AB04 AB07 AB08 AB09 AB17                       AB19 AB28 AB31 AB34 AB40                       AC04 AC05 BA28 BA50 DB36                       GA07

Claims (7)

[Claims] 1. A plurality of columnar spacers are provided in a non-display area on a substrate, and the columnar spacers have an elastic deformation rate [(elastic deformation amount / total deformation amount) with respect to a compressive load of 2.0 GPa at room temperature. × 100] is 60% or more, a liquid crystal panel substrate. 2. A color filter comprising a pixel portion provided in a display area of the substrate.
The substrate for a liquid crystal panel described in. 3. A liquid crystal panel in which a display side substrate and a liquid crystal driving side substrate are opposed to each other and liquid crystal is sealed between the both, wherein at least one of the display side substrate and the liquid crystal driving side substrate is said. A liquid crystal panel, which is the substrate for a liquid crystal panel according to 1 or 2. 4. The liquid crystal panel according to claim 3, wherein the display side substrate is a color filter and is constituted by the liquid crystal panel substrate according to claim 2. 5. A photocurable resin composition for pattern formation, which comprises at least a polyfunctional acrylate monomer, a polymer and a photopolymerization initiator, and the content of the polyfunctional acrylate monomer is 50% by weight or more. Resin composition of 2.0 GPa at room temperature after curing
Elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] is 60% or more with respect to the compressive load of
Photocurable resin composition. 6. The photocurable resin composition according to claim 5, which is used for forming a columnar spacer provided in a non-display area on a liquid crystal panel substrate. 7. The photocurable resin composition according to claim 5, wherein at least a part of the polyfunctional acrylate monomer has one or more acidic groups and three or more ethylenically unsaturated bonds.