JP2003173025A - Curable resin for forming photosensitive pattern, method for producing the same, curable resin composition, color filter, substrate for liquid crystal panel and liquid crystal panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin and a curable resin composition capable of freely regulating alkali solubility and curability and having high sensitivity, to provide substrates for a liquid crystal panel capable of retaining a uniform cell gap and to provide a liquid crystal panel using the substrates and excellent in display quality. <P>SOLUTION: The curable resin composition contains a curable resin comprising an imido-containing copolymer having a molecular structure in which a constitutional unit having a cyclic imido group of formula (1), a constitutional unit having an acidic functional group such as a carboxyl group and a constitutional unit having a photopolymerizable functional group are linked. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin for forming a photosensitive pattern, a method for producing the same, a curable resin composition for forming a photosensitive pattern containing the curable resin for forming a photosensitive pattern, and the photosensitive material. The present invention relates to a color filter using a curable resin composition for pattern formation, a liquid crystal panel substrate capable of maintaining a uniform cell gap, and a liquid crystal panel excellent in display quality using the color filter or 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) (primary colors) are arranged in a predetermined order or a colored layer using a hologram these days, a protective film 8, and a transparent electrode film 9 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. Further, in the gap portion 3, in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2, spherical or rod-shaped particles 11 made of glass, alumina, plastic or the like having a certain size are used as spacers.
Are distributed. Then, a color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color filter.

Protective film 8 formed on the color filter
Plays a role of protecting the colored layer and flattening the color filter when the colored layer is provided on the color filter. In a color liquid crystal display device, gap unevenness, R, and G caused by the undulation of the transparent substrate surface of the color filter
If the flatness of the transparent electrode film 9 is impaired due to the presence of gap unevenness between pixels of B and B or the presence of gap unevenness within each pixel, color unevenness or contrast unevenness occurs, and as a result, image quality deteriorates. I have the problem of calling you. Therefore, the protective film is required to have high flatness.

When the fine particles 11 shown in FIG. 1 are dispersed as a spacer, the fine particles 11 are randomly dispersed regardless of whether they are behind the black matrix layer 6 or behind the pixels. When the fine particles 11 are arranged in the display area, that is, the colored layer, the light of the backlight is transmitted through the fine particles 11, and the alignment of the liquid crystal around the fine particles 11 is disturbed, which significantly deteriorates the quality of the display image. Therefore, as shown in FIG. 2, instead of dispersing the fine particles 11, a region (non-display region) on the inner surface side of the color filter which overlaps with the position where the black matrix layer 6 is formed corresponds to the cell gap. It has become common practice to form columnar spacers 12 having a height.

The colored layer 7, the protective film 8 and the columnar spacer 12 can be formed of resin. The colored layer 7 needs to be formed in a predetermined pattern for each color pixel. Considering the adhesiveness and hermeticity of the seal portion, the protective film 8 is preferably a film that can cover only the region of the transparent substrate where the colored layer is formed. Further, the columnar spacers 12 need to be accurately provided in the area where the black matrix layer is formed, that is, in the non-display area. For this reason,
It has been proposed to form a colored layer, a protective film, and a columnar spacer using a photocurable resin that can be alkali-developed after selectively exposing a region to be cured.

As an alkali-soluble photocurable resin, for example, o-cresol novolac epoxy acrylate having a weight average molecular weight of about 2,000 and having a carboxylic acid group which defines alkali solubility is known. However, since this resin uses a monomer component as an acryloyl group that regulates curability, reliability during film formation is low, and residual monomer units may elute into the liquid crystal part, for example. The amount of elution during development is large, and the film may be reduced.

Further, as a method of introducing a radically polymerizable group such as an acryloyl group into the molecular structure of the compound in order to impart photocurability, for example, diols are reacted with an excess of diisocyanate, and isocyanate is added to the end. By preparing a reaction leaving a group and reacting the isocyanate group of this reaction with 2-hydroxylethylmethacrylate or the like to form a urethane acrylate,
A method of introducing a radically polymerizable group such as a methacryloyl group into the terminal is known. However, with this method,
In principle, (meth) acryloyl groups are introduced only at both ends of the molecular structure. Further, a method of radically polymerizing a polyfunctional compound having two or more radically polymerizable groups such as (meth) acryloyl group in one molecule may be considered, but it is not possible to control the content of the radically polymerizable group. It cannot be done and there is a problem such as gelation.

Therefore, the present inventors have a main chain composed of at least a constitutional unit represented by the following formula (14) and a constitutional unit represented by the following formula (15), and A photocurable resin in which a (meth) acryloyloxyalkylisocyanate compound represented by the following formula (16) is bound at least in part by the reaction of the isocyanate group of the compound has been proposed, and a patent application has already been made (JP 2000 -105456).

[0011]

[Chemical 9]

[0012]

[Chemical 10]

[0013]

[Chemical 11]

(In each formula, R ²⁰ is hydrogen or has 1 to 5 carbon atoms.
Alkyl group, R ²¹ is an alkylene group having 2 to 4 carbon atoms, R ^21
22 represents an alkylene group, and R ²³ represents hydrogen or methyl. ) The photocurable resin according to the above proposal has an advantage that the amount of an alkali-soluble carboxyl group and a radical-polymerizable (meth) acryloyl group can be freely adjusted, but it cannot be said that the sensitivity is sufficient, A relatively large amount of photoinitiator is required for rapid curing even with a small exposure amount. However, when a large amount of the photoinitiator is used, the resin is likely to be colored, the effect as an impurity becomes large, which causes liquid crystal contamination in particular, or bleeds out on the surface of the coating film to impair the physical properties of the film. It causes inconvenience.

Further, the columnar spacers formed by using the conventional photo-curable resin used for photolithography are plastically deformed under high temperature and high pressure at the time of assembly (cell pressure bonding) of the color filter and the TFT array substrate, and the predetermined size is obtained. There is a problem in that the function as a spacer is hindered, for example, the cell gap in the distance cannot be maintained evenly and display unevenness occurs.

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.
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.

In addition, in recent years, the area of liquid crystal display devices has been increased, and the need for 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, due to the recent expansion 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 for the cell gap are becoming more and more stringent.

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. The liquid crystal is filled and sealed in the cell gap by utilizing the pressure difference of 1. However, as the display area is enlarged and the cell gap is narrowed, it becomes difficult to fill the liquid crystal smoothly. 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.

On the other hand, Japanese Patent Laid-Open No. 6-82620 discloses that
Photocrosslinking property obtained by copolymerizing a monomer (a) having a cyclic imide group, a monomer (b) having an acidic group such as (meth) acrylic acid, and a monomer (c) different from the monomers (a) and (b) It is described that a layer containing a polymer is exposed to form a protective layer of a color filter. According to this publication, the protective layer for a color filter obtained by using the proposed photocrosslinkable polymer is said to have excellent adhesion, heat resistance and chemical resistance.

Further, in JP-A-2000-235259, a compound having an ethylenically unsaturated group and a cyclic imide group, a copolymer (A) having an ethylenically unsaturated monomer as a constitutional unit, and two or more are included. The active energy ray-curable resist mainly composed of a compound having a (meth) acryloyl group is used as a solder resist, an etching resist, and a plating resist. According to this publication, the proposed active energy ray-curable resist is easily cured by active energy rays, and even when it is cured by ultraviolet rays, a photopolymerization initiator is not added at all or a small amount is used for excellent curing. In addition to having properties, the cured product is said to have excellent heat resistance and chemical resistance.

[0025]

SUMMARY OF THE INVENTION The present invention has been accomplished in view of such circumstances, and the first object thereof is high sensitivity in addition to the ability to freely adjust alkali solubility and curability. It is an object of the present invention to provide a curable resin that can be rapidly cured with a small exposure amount even if a small amount of a photoinitiator is used.

A second object of the present invention is to provide a method for producing the curable resin according to the present invention.

A third object of the present invention is that the solubility and curability of the alkali can be freely adjusted, and that the composition has high sensitivity and can be rapidly cured with a small exposure amount even if a small amount of photoinitiator is used. It is to provide a curable resin composition capable of

A fourth 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 to prevent plastic deformation during cell pressure bonding and subsequent handling, and the liquid crystal heat resistance. It is intended to provide a photosensitive resin composition for forming a pattern, which is capable of forming a spacer having flexibility that can follow a constant contraction and expansion.

A fifth object of the present invention is to provide a color filter which hardly causes yellowing.

A sixth object of the present invention is to provide a spacer having sufficient hardness that is not easily plastically deformed during cell pressure bonding and subsequent handling, and suppleness capable of following thermal contraction and expansion of liquid crystal. An object of the present invention is to provide a liquid crystal panel substrate that is provided with a cell gap that can be formed accurately and uniformly.

A seventh object of the present invention is to provide a 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. An object of the present invention is to provide a substrate for a liquid crystal panel which can cope with an expansion and a narrowing of a cell gap.

An eighth 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 liquid crystal panel substrate provided with a spacer.

A ninth object of the present invention is to provide a liquid crystal panel using the color filter or the liquid crystal panel substrate according to the present invention, which is excellent in display quality.

[0034]

The curable resin for forming a photosensitive pattern provided in the present invention comprises at least a structural unit having a cyclic imide group represented by the following formula (1) and an acidic functional group. The constitutional unit provided, and a photopolymerizable functional group excluding the cyclic imide group (hereinafter, simply "photopolymerizable functional group"
The imide group-containing copolymer having a molecular structure in which a constitutional unit having a) is connected.

[0035]

[Chemical 12]

(In the formula, R ³ and R ⁴ are each independently an alkyl group having 4 or less carbon atoms, or either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or Each is a group that forms a carbocycle together.) In the molecular structure of the imide group-containing copolymer, an acidic functional group-containing unit and a photopolymerizable functional group-containing unit are contained together with the cyclic imide group-containing unit. Therefore, excellent photopolymerization reactivity and alkali solubility are obtained.

The constitutional unit having the photopolymerizable functional group is
It preferably has an ethylenically unsaturated bond as a photopolymerizable functional group. The ethylenically unsaturated bond can form a cross-linking bond with the cyclic imide group represented by Formula 1 by photoradical polymerization.

In one embodiment, the imide group-containing copolymer is a structural unit represented by the following formula (4) or a structural unit represented by the following formula (5) as a structural unit having a photopolymerizable functional group. It is possible to use those containing the structural unit described above.

[0039]

[Chemical 13]

(In the formula, R ⁶ and R ⁷ are a hydrogen atom or a methyl group.)

[0041]

[Chemical 14]

(In the formula, R ⁸ and R ¹¹ are a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 2 to 4 carbon atoms, and R ¹⁰ is an alkylene group.) In another embodiment, As the imide group-containing copolymer, a constitutional unit represented by the following formula (2) as a constitutional unit having a cyclic imide group, and a constitutional unit represented by the following formula (3) as a constitutional unit having an acidic functional group are shown. It is possible to use those containing a structural unit.

[0043]

[Chemical 15]

(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 6 carbon atoms, and R ³ and R ⁴ are the same as above.)

[0045]

[Chemical 16]

(In the formula, R ⁵ is a hydrogen atom or a methyl group.) Further, the imide group-containing copolymer preferably has an alcoholic hydroxyl group in the molecule.

In order to produce a curable resin comprising the above imide group-containing copolymer, first, at least a constitutional unit having a cyclic imide group represented by the formula (1) and an acidic functional group are provided. A polymer having a main chain composed of a structural unit and a structural unit having a functional group capable of introducing a pendant structure having a photopolymerizable functional group (raw polymer) is produced, and then photopolymerized to the raw polymer. A pendant structure of a photopolymerizable functional group may be introduced by reacting a compound having a functional group with another functional group.

In one embodiment, at least a structural unit having a cyclic imide group represented by the above formula (1),
By reacting a raw material polymer having a molecular structure in which a structural unit having an acidic functional group is linked with glycidyl acrylate and / or glycidyl methacrylate,
The curable resin for forming a photosensitive pattern of the present invention can be produced.

In another embodiment, the above formula (1)
In a raw material polymer having a molecular structure in which a constitutional unit having a cyclic imide group represented by, a constitutional unit having an acidic functional group, and a constitutional unit having a hydroxyl group are linked, a compound represented by the following formula (6) The curable resin for photosensitive pattern formation of the present invention can be produced by reacting the isocyanate compound.

[0050]

[Chemical 17]

(In the formula, R ¹⁰ is an alkylene group, and R ¹¹
Is a hydrogen atom or a methyl group. The curable resin composition for forming a photosensitive pattern provided in the present invention is characterized by containing the curable resin for forming a photosensitive pattern according to the present invention as an essential component.

When the curable resin composition for forming a photosensitive pattern of the present invention is applied to any support to form a coating film, and the coating film is irradiated with an activation energy ray such as ultraviolet rays or ionizing radiation, an imide group is formed. The photopolymerizable functional group or cyclic imide group of the contained copolymer, and the polyfunctional polymerizable compound such as a bifunctional or higher functional acrylic monomer cause a photoradical polymerization reaction, and the dimerization reaction between the cyclic imide groups occurs. By causing this, cross-linking bonds are formed between the molecules of the imide group-containing copolymer, and the copolymer is cured.

In this curable resin composition, the photopolymerizable functional group and the cyclic imide group coexist in the molecule of the imide group-containing copolymer as the main polymer, and the reactivity of the cyclic imide group is high. Since the cross-linking reaction has a high reaction point density, the exposure sensitivity is very high and it is possible to cure with a small exposure amount or an extremely short exposure time by using a small amount of a photopolymerization initiator. Therefore, the time required for pattern formation can be shortened, and the energy for exposure and the amount of photopolymerization initiator used can be saved. Also,
After curing, since the amount of the photopolymerization initiator used is small, yellowing of the cured product, particularly yellowing when used as a protective film or a coloring layer of a color filter, is unlikely to occur, resulting in excellent transparency. Further, the photosensitive pattern forming curable resin composition of the present invention, the cyclic imide group contributes to the crosslinking reaction, the reaction site density of the crosslinking reaction is high, the coating strength after curing, heat resistance, It has excellent physical properties such as chemical resistance.

The curable resin composition for forming a photosensitive pattern of the present invention forms a colored layer of a color filter, a protective film covering the colored layer, and a columnar spacer for maintaining a cell gap of a liquid crystal panel. Suitable for
It is possible to form a colored layer having a desired film thickness, a protective film, and a columnar spacer having a desired height with high precision, and it is also excellent in transparency after curing and other physical properties.

In one embodiment, the curable resin for forming a photosensitive pattern is 2.0 GP at room temperature after curing.
The elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] with respect to the compressive load of a can be set to 60% or more. In this case, it can be used as a pattern forming material that exhibits a large elastic deformation rate and a small plastic deformation rate at room temperature after curing, and can be particularly preferably used for forming a convex spacer of a liquid crystal panel. .

The crosslinking density can be improved by blending the above-mentioned curable resin composition with a photopolymerizable compound having two or more photopolymerizable functional groups. The photopolymerizable compound preferably has an ethylenically unsaturated bond as a photopolymerizable functional group. The photopolymerizable compound having two or more ethylenically unsaturated bonds can form a crosslink also with the cyclic imide group and the ethylenically unsaturated bond of the imide group-containing copolymer.

Further, the photopolymerizable compound blended in the curable resin composition is a photopolymerizable compound having an alcoholic hydroxyl group together with three or more ethylenically unsaturated bonds to enhance the reactivity. It is preferable from the viewpoint of improving sensitivity and curability.

If necessary, a photopolymerization initiator may be added to the above curable resin composition.

The color filter provided in the present invention comprises a transparent substrate and a colored layer provided on the transparent substrate, and further comprises a protective film covering the colored layer and / or a non-display area of the substrate. A spacer may be provided, and at least one of the colored layer, the protective film and the spacer is formed by curing the curable resin composition for forming a photosensitive pattern. And

In the color filter of the present invention, since the colored layer, the protective film or the spacer is formed by using the curable resin composition for forming a photosensitive pattern according to the present invention, the colored layer and the protective film have high transparency. , Yellowing is hard to occur,
The accuracy and uniformity of the colored layer, protective film and spacer are also high.

The liquid crystal panel substrate according to the present invention is provided with a plurality of spacers in a non-display area on the substrate, and the spacers are formed by curing the resin composition according to the present invention. Elastic deformation ratio [(elastic deformation amount / total deformation amount) × compressed load of 2.0 GPa at room temperature ×
100] is 60% or more.

The spacers have sufficient hardness that they are not easily plastically deformed by a compressive load at room temperature, and are supple enough 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, pressure unevenness is alleviated or absorbed so that the load is made uniform over the entire substrate to eliminate 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 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,
Even if the display area of the liquid crystal display device is large or the cell gap is very narrow, the cell gap can be maintained accurately and uniformly.

The 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 can form an accurate and uniform cell gap without causing plastic deformation when laminating by a room temperature cell pressure bonding method. 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.

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 driving side substrate are opposed to each other and liquid crystal is sealed between them, At least one of the side substrates is the color filter or the liquid crystal panel substrate according to the present invention.

The liquid crystal panel according to the present invention is excellent in the transparency and heat resistance of the display portion and is hard to cause the yellowing phenomenon.
Since the cell gap can be accurately and uniformly maintained during cell pressure bonding and subsequent handling, display unevenness hardly occurs and display quality is excellent.

[0069]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. In the present invention, (meth) acrylic means either an acrylic group or a methacrylic group, a (meth) acrylate means either an acrylate or a methacrylate, and a (meth) acryloyl Means either an acryloyl group or a methacryloyl group.

The curable resin for forming a photosensitive pattern provided by the present invention comprises at least a constitutional unit having a cyclic imide group represented by the following formula (1), a constitutional unit having an acidic functional group, and It contains an imide group-containing copolymer having a molecular structure in which a structural unit having a photopolymerizable functional group is linked.

[0071]

[Chemical 18]

(In the formula, R ³ and R ⁴ are each independently an alkyl group having 4 or less carbon atoms, or either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or Each of them is a group that forms a carbocycle together.) The structural unit (cyclic imide group-containing unit) having a cyclic imide group represented by the formula (1) has a photocuring reaction sensitivity and a cured coating. It is a component that contributes to the heat resistance and chemical resistance of the film, the elastic deformation rate and the total deformation rate at room temperature after curing, and other physical properties. The content ratio is adjusted in consideration of these physical properties, particularly the degree of sensitivity required for the curable resin, and the elastic deformation rate at room temperature and the total deformation rate when used as a spacer. As the monomer used for introducing the cyclic imide group-containing unit into the main chain of the polymer, use a compound having an ethylenically unsaturated bond for forming a main chain linkage together with the cyclic imide group. You can

Examples of the cyclic imide group represented by the formula (1) include those represented by the following formulas (1a) to (1c).

[0074]

[Chemical 19]

The constitutional unit having a cyclic imide group represented by the formula (1) is represented by the following formulas (7a) to (7c).
What is represented by can be illustrated. By linking the structural units represented by formulas (7a) to (7c) to other main chain structural units, a pendant structure containing a cyclic imide group can be introduced into the copolymer molecule.

[0076]

[Chemical 20]

(In the formula, R ¹ is a hydrogen atom or a methyl group. As described above, R ³ and R ⁴ are each independently an alkyl group having 4 or less carbon atoms, or either one is a hydrogen atom and the other is a hydrogen atom. Is an alkyl group having 4 or less carbon atoms, or
Each is a group that forms a carbocycle. R
¹² is an alkylene group having 1 to 6 carbon atoms, and n is an integer of 1 to 6. R ¹³ is a cycloalkylene group. R ¹⁴ is an alkylene group or a cycloalkylene group. R ¹⁵ is a hydrogen atom or an alkyl group. Among these structural units, the cyclic imide group-containing unit represented by the following formula (2) is preferable.

[0078]

[Chemical 21]

(In the formula, R ¹ is a hydrogen atom or a methyl group as described above. R ² is an alkylene group having 1 to 6 carbon atoms. R ³ and R ⁴ have independent carbon numbers as described above. An alkyl group having 4 or less, one of which is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or each of which is a group forming a carbocycle. A structural unit (unit containing an acidic functional group)
Is a component that contributes to alkali solubility, and the content ratio thereof is adjusted depending on the degree of alkali solubility required for the curable resin. As the monomer used for introducing the constituent unit having an acidic functional group into the main chain of the imide group-containing copolymer, a compound having an ethylenically unsaturated bond and an acidic functional group can be used. . The acidic functional group is usually a carboxyl group, but any component other than the carboxyl group may be used as long as it can contribute to alkali solubility.

As the constitutional unit having an acidic functional group, a constitutional unit represented by the following formula (3) is preferable.

[0081]

[Chemical formula 22]

(In the formula, R ⁵ is a hydrogen atom or a methyl group.) Acrylic acid or methacrylic acid can be used as the monomer used for introducing the structural unit of the formula (3). .

The constitutional unit having a photopolymerizable functional group (photopolymerizable functional group-containing unit) contributes to the photocurability of the resin together with the constitutional unit containing the cyclic imide group represented by the above formula (1). It is a component, and the content ratio thereof is adjusted depending on the degree of photocurability required.

As the photopolymerizable functional group, various reaction types such as photoradical polymerization, photocationic polymerization, photoanionic polymerization and the like can be used, and a photopolymerizable photopolymerizable with the cyclic imide group represented by the formula 1 can be used. A radically polymerizable functional group is preferable, and an ethylenically unsaturated bond is particularly preferable.

In order to introduce the photopolymerizable functional group-containing unit into the main chain of the imide group-containing copolymer, a compound having an ethylenically unsaturated bond and a photopolymerizable functional group may be used in some cases. Depending on the type of the photopolymerizable functional group, the photopolymerizable functional group may also be copolymerized together under the reaction conditions for forming the main chain linkage of the imide group-containing copolymer. For example, when it is desired to introduce a structural unit having an ethylenically unsaturated bond as a photopolymerizable functional group, both the functional group forming the main chain linkage and the photopolymerizable functional group are ethylenically unsaturated bonds, Even if an attempt is made to form a main chain linkage of an imide group-containing copolymer by using a monomer having two or more ethylenically unsaturated bonds, a crosslinking reaction occurs, so it is difficult to introduce the desired structural unit. Is. Therefore,
The photopolymerizable functional group is preferably introduced into the main chain of the copolymer through an appropriate functional group after forming the main chain connection of the imide group-containing copolymer.

A constitutional unit having an ethylenically unsaturated bond as a photopolymerizable functional group (unit containing an ethylenically unsaturated bond)
Is preferably represented by the following formula 4.

[0087]

[Chemical formula 23]

(In the formula, R ⁶ and R ⁷ are a hydrogen atom or a methyl group.) In order to introduce the structural unit of the formula (4) into the imide group-containing copolymer, first, a cyclic imide group-containing monomer is introduced. After copolymerizing the monomer and (meth) acrylic acid to form the main chain portion of the imide group-containing copolymer, glucidyl (meth) acrylate may be reacted with the carboxyl group derived from the (meth) acrylic acid. . However, when the amount of carboxyl groups derived from (meth) acrylic acid is too small, the alkali solubility is insufficient, so it is necessary to appropriately adjust the amount of glycidyl (meth) acrylate.

As the ethylenically unsaturated bond-containing unit, a constitutional unit represented by the following formula (5) is also one of the preferable ones.

[0090]

[Chemical formula 24]

(In the formula, R ⁸ and R ¹¹ are a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 2 to 4 carbon atoms, and R ¹⁰ is an alkylene group.) Included in the formula (5). R ⁹ is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a butylene group. R ¹⁰ is preferably an alkylene group having 2 to 6 carbon atoms.

In order to introduce the constitutional unit of the formula (5) into the imide group-containing copolymer, first, a hydroxy imide represented by the following formula (8) is used together with the cyclic imide group-containing monomer and (meth) acrylic acid. The alkyl (meth) acrylate is copolymerized to form the main chain portion of the imide group-containing copolymer.

[0093]

[Chemical 25]

(In the formula, R ⁸ and R ⁹ are the same as those in the formula (5).) As the hydroxyalkyl (meth) acrylate of the formula (8), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 -Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like are exemplified.

Thereafter, the hydroxyalkyl (meth)
A hydroxyl group derived from acrylate may be reacted with an isocyanate compound represented by the following formula (6).

[0096]

[Chemical formula 26]

(In the formula, R ¹⁰ is an alkylene group, and R ¹¹
Is a hydrogen atom or a methyl group. In the (meth) acryloyloxyalkyl isocyanate of the formula (6), the (meth) acryloyl group is an isocyanate group (-N) via an alkylene group having 2 to 6 carbon atoms.
It is preferred to use the one combined with CO). Specifically, 2-acryloyloxyethyl isocyanate,
2-methacryloyl ethyl isocyanate etc. are illustrated. 2-methacryloylethyl isocyanate is commercially available under the trade name of "Karenzu MOI" manufactured by Showa Denko KK, for example.

The imide group-containing copolymer contained in the curable resin for forming a photosensitive pattern provided by the present invention is
A structural unit having a cyclic imide group represented by formula (1),
The constitutional unit having an acidic functional group and the constitutional unit having a photopolymerizable functional group are contained as essential constituent components of the main chain, but other copolymerization components may be contained in the main chain. The main chain may contain, for example, a constitutional unit having an alcoholic hydroxyl group, a constitutional unit having an aromatic carbon ring, and / or a constitutional unit having an ester group.

Structural unit having alcoholic hydroxyl group (alcoholic hydroxyl group-containing unit, for example, alcoholic hydroxyl group-containing methylene group or alcoholic hydroxyl group-containing methine group)
Is a structural unit which, when photocuring the curable resin, generates a radical by the hydrogen abstraction effect of the cyclic imide group to increase the reactivity of the cyclic imide group and the alcoholic hydroxyl group-containing unit. As a monomer used for introducing a structural unit having an alcoholic hydroxyl group into the main chain of an imide group-containing copolymer, a compound having an ethylenically unsaturated bond and an alcoholic hydroxyl group can be used. .
The alcoholic hydroxyl group may be contained in the cyclic imide group-containing unit.

As the alcoholic hydroxyl group-containing unit, a structural unit represented by the following formula (9) is preferable.

[0101]

[Chemical 27]

(In the formula, R ⁸ and R ⁹ are the same as those in the formula (5).) The monomer used for introducing the constitutional unit of the formula (9) is represented by the above formula (8). The hydroxyalkyl (meth) acrylates represented can be used. As described above, the hydroxyalkyl (meth) acrylate represented by the formula (8) is reacted with the ethylenically unsaturated bond-containing isocyanate compound represented by the (meth) acryloyloxyalkyl isocyanate of the formula (6) to obtain ethylene. It is also used to introduce sexually unsaturated bonds. Therefore, after the hydroxyalkyl (meth) acrylate represented by the following formula (8) is copolymerized with the cyclic imide group-containing monomer and (meth) acrylic acid to form the main chain portion of the imide group-containing copolymer. The imide group-containing copolymer having a hydroxyl group and an ethylenically unsaturated bond can be obtained by appropriately controlling the amount of the ethylenically unsaturated bond-containing isocyanate compound in the hydroxyl group of the pendant structure portion to carry out the reaction.

When the curable resin is used for forming a coating film such as a protective film of a color filter, the constitutional unit having an aromatic carbon ring (aromatic carbon ring-containing unit) has a coating property on the curable resin. Is a component that imparts. As the monomer used for introducing the aromatic carbocyclic unit into the main chain of the polymer, a compound having a double bond-containing group and an aromatic carbocyclic ring can be used.

The aromatic carbon ring-containing unit is preferably a constitutional unit represented by the following formula (10).

[0105]

[Chemical 28]

(In the formula, R ¹⁶ represents a hydrogen atom or a methyl group, and R ¹⁷ represents an aromatic carbocycle.) R ¹⁷ contained in the formula (10) is an aromatic carbocycle, for example, phenyl. Examples thereof include groups and naphthyl groups. Expression (1
Examples of the monomer used for introducing the structural unit of 0) include styrene and α-methylstyrene, and the aromatic ring thereof has a halogen atom such as chlorine and bromine, a methyl group, It may be substituted with an alkyl group such as an ethyl group, an amino group, an amino group such as a dialkylamino group, a cyano group, a carboxyl group, a sulfonic acid group, or a phosphoric acid machine.

The structural unit having an ester group (ester group-containing unit) is a component that suppresses the alkali solubility of the curable resin. As the monomer used for introducing the ester group-containing unit into the main chain of the polymer, a compound having a double bond-containing group and an ester group can be used.

As the ester group-containing unit, the following formula (1
Those represented by 1) are preferable.

[0109]

[Chemical 29]

(In the formula, R ¹⁸ is a hydrogen atom or a methyl group, and R ¹⁹ is an alkyl group or an aralkyl group.) R ¹⁹ contained in the formula (11) is an alkyl group or an aralkyl group. Examples thereof include an aralkyl group such as an alkyl group having 1 to 12 carbon atoms, a benzyl group and a phenylethyl group. Examples of the monomer used to introduce the structural unit of the formula (11) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenyl. (Meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth)
Acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate,
Examples are (meth) acrylic acid esters such as benzyl (meth) acrylate and phenylethyl (meth) acrylate.

The monomer used to introduce each constituent unit into the main chain of the cyclic imide group-containing copolymer may be one of the exemplified constituents, or two or more kinds. You may mix and use.

As a particularly preferable cyclic imide group-containing copolymer, a random copolymer or a block copolymer represented by the following formula (12) or the following formula (13) is exemplified. it can. The main chain of these copolymers may contain other main chain constituent units, if necessary.

[0113]

[Chemical 30]

(In the formula, R ^{1 to} R ⁷ are the same as described above. L, m and n are integers.)

[0115]

[Chemical 31]

(In the formula, R ^{1 to} R ⁵ and R ^{8 to} R ¹¹ are the same as described above. L, m and n are integers.) In the present invention, the molecule of the imide group-containing copolymer is used. The content ratio of each structural unit constituting the structure is appropriately adjusted, but if the content ratio of the cyclic imide group-containing unit is too small, the sensitivity of the photocuring reaction is not sufficiently improved, especially in the case of forming a spacer. It becomes difficult to control the elastic deformation rate and the total deformation rate at room temperature after curing within a favorable range. On the other hand, when the content ratio of the cyclic imide group-containing unit is too large, only the curing of the coating film surface is promoted, and the interior of the coating film is not sufficiently cured. Further, when the amount of the acidic functional group-containing unit is too small, alkali solubility becomes insufficient, and when it is too large, there is a problem that the solvent solubility decreases. Also,
If the amount of the photopolymerizable functional group-containing unit is too small, the curability becomes insufficient, while if the number of the structural units having an ethylenically unsaturated bond as the photopolymerizable functional group is too large, the substrate adhesion is lowered. There's a problem.

Specifically, the content ratio of the cyclic imide group-containing unit in the imide group-containing copolymer is 10 mol% to 90 mol%, and particularly 40 mol% to, in terms of the charged amount as a monomer.
By adjusting in the range of 80 mol%, the elastic deformation rate,
It is possible to optimize the physical properties related to the cyclic imide group-containing unit such as the total deformation rate and the photocuring reactivity.

Specifically, in the case of the copolymer of the above formula (12), the cyclic imide group-containing unit is in an amount of about 10 mol% to 90 mol% in terms of the charged amount as a monomer, and an acidic functional group. About 5 mol% to 85 mol% of (meth) acrylic acid as a pendant connecting site of a group-containing unit and an ethylenically unsaturated bond, and glycidyl acid (meth) acrylate as a pendant introducing unit of an ethylenically unsaturated bond 5
It is set to about mol% to 45 mol%.

In the case of the copolymer of the above formula (13), the cyclic imide group-containing unit is about 10 mol% to 90 mol% and the acidic functional group-containing unit in terms of the charged amount as a monomer. (Meth) acrylic acid as about 8 mol% to 88 mol%, and a hydroxyalkyl (meth) acrylate as a pendant connecting site of an alcoholic hydroxyl group-containing unit and an ethylenically unsaturated bond is about 1 mol% to 81 mol%, And 1 mol% to 45 mol% of an isocyanate compound as a pendant introduction unit of an ethylenically unsaturated bond.
The degree.

In order to produce the above imide group-containing copolymer, first, a structural unit having a cyclic imide group represented by the formula (1) and an acidic functional group represented by the formula (3) are used. A constitutional unit, a constitutional unit having a functional group into which a pendant structure having a photopolymerizable functional group can be introduced later, and, if necessary, a constitutional unit represented by the formula (9) having an alcoholic hydroxyl group, an aromatic compound. A polymer having a main chain containing a constitutional unit such as formula (10) having a group carbocycle, a constitutional unit such as formula (11) having an ester group, or another constitutional unit (raw polymer) ) Is produced, and then a compound having some other functional group together with a photopolymerizable functional group such as an ethylenically unsaturated bond is reacted with the raw material polymer to introduce a pendant structure of the photopolymerizable functional group. Good.

However, as in the case of using a constitutional unit such as formula (3) having a carboxyl group as the acidic functional group-containing unit and using glycidyl (meth) acrylate as the photopolymerizable functional group-containing unit, an acidic functional group is used. When the group-containing unit also functions as a pendant linking site of the photopolymerizable functional group, the main chain of the raw material polymer is a functional group capable of introducing a photopolymerizable functional group later, separately from the acidic functional group-containing unit. May not contain a structural unit having

Further, in order to improve the sensitivity of the cyclic imide group, a formula (6) containing an alcoholic hydroxyl group-containing unit in the main chain of the raw material polymer and an ethylenically unsaturated bond as a photopolymerizable functional group-containing unit In the case where an alcoholic hydroxyl group-containing unit or other additional structural unit also functions as a pendant linking site of the photopolymerizable functional group-containing unit, as in the case of using an isocyanate compound such as The main chain does not have to include a structural unit having a functional group into which a photopolymerizable functional group can be introduced later, in addition to those additional structural units.

The solvent for polymerization used for producing the raw material polymer is preferably a solvent having no active hydrogen such as hydroxyl group and amino group, for example, ethers such as tetrahydrofuran; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol. Glycol ethers such as methyl ethyl ether, cellosolve esters such as methyl cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc., and aromatic hydrocarbons, ketones, esters, etc. should also be used. You can

As the polymerization initiator used for producing the raw material polymer, those generally known as radical polymerization initiators can be used. Specific examples thereof include 2,2′-azobisisobutyronitrile,
2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-
Nitrile azo compounds such as dimethyl valeronitrile) (nitrile azo polymerization initiators); dimethyl 2,2'-
Non-nitrile azo compounds (non-nitrile azo polymerization initiator) such as azobis (2-methylpropionate) and 2,2′-azobis (2,4,4-trimethylpentane);
t-hexyl peroxypivalate, tert-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,
1,3,3-Tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-
Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, 4-methylbenzoyl peroxide, Benzoyl peroxide, 1,
Examples thereof include organic peroxides (peroxide-based polymerization initiators) such as 1′-bis- (tert-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be used in combination with a reducing agent as a redox type polymerization initiator.

In the production of the raw material polymer, a molecular weight modifier may be used for controlling the weight average molecular weight, and examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-
Mercaptans such as dodecyl mercaptan and thioglycolic acid; xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

The raw material polymer may be either a random copolymer or a block copolymer. In the case of producing a random copolymer, the compounded composition containing each monomer for inducing each structural unit, a catalyst and the like is mixed in a polymerization tank containing a solvent at a temperature of 80 to 110 ° C. Polymerization can be carried out by adding dropwise over 5 hours and aging.

The polystyrene-equivalent weight average molecular weight (hereinafter simply referred to as "weight average molecular weight" or "Mw") of the raw material polymer is in the range of 1,000 to 1,000,000, and particularly 3 in the case of forming a spacer. , 000-1,00
The acid value is 5mgKOH /
g-400 mgKOH / g, hydroxyl value is 5 mgKOH / g
It is preferably from g to 400 mg KOH / g.

The reaction of introducing a photopolymerizable functional group such as an ethylenically unsaturated bond into the raw material polymer depends on the combination of the molecular structure of the raw material polymer and the molecular structure of the unit into which the photopolymerizable functional group is introduced. Are various.

A raw material polymer comprising a cyclic imide group-containing unit represented by the formula (2) and a carboxyl group-containing unit represented by the formula (3) and optionally other constitutional units is added with an ethylenic When reacting glycidyl (meth) acrylate as a unit for introducing a saturated bond, the glycidyl (meth) acrylate is reacted in the presence of a small amount of a catalyst for a certain period of time after the entire amount of the glycidyl (meth) acrylate is added to the solution of the raw material polymer at once. , Or by dripping little by little,
A curable resin composed of the imide group-containing copolymer represented by the formula (12) is obtained.

Further, a cyclic imide group-containing unit represented by the formula (2), a carboxyl group-containing unit represented by the formula (3) and a hydroxyl group-containing unit represented by the formula (9) are contained, and the unit may be added as required. When a raw material polymer containing another constituent unit is reacted with an isocyanate compound represented by the formula (6) as an introduction unit of an ethylenically unsaturated bond, the isocyanate compound is used as a raw material in the presence of a small amount of a catalyst. A curable resin composed of an imide group-containing copolymer represented by the formula (13), which is obtained by adding the whole amount to a polymer solution at once and then continuing the reaction for a certain period of time or by dropping little by little. Is obtained. In this case, dibutyltin laurate or the like is used as the catalyst, and a polymerization inhibitor such as p-methoxyphenol, hydroquinone, naphthylamine, tert-butylcatechol, 2,3-di-tert-butyl p-cresol is required. Used according to.

The isocyanate compound having an ethylenically unsaturated bond undergoes an addition reaction with the alcoholic hydroxyl group of the raw material polymer through the isocyanate group to form a urethane bond. As a result, an ethylenically unsaturated bond is introduced into the portion of the hydroxyl group-containing unit represented by formula (9) in the main chain of the raw material polymer, and the constitutional unit of formula (5) is formed.

Further, the isocyanate compound having an ethylenically unsaturated bond causes a condensation reaction involving desorption of carbon dioxide gas with respect to the carboxyl group of the raw material polymer through the isocyanate group to form an amide bond. As a result, the ethylenically unsaturated bond is also introduced into the portion of the carboxyl group-containing unit represented by the formula (3) in the main chain of the raw material polymer. However, the reactivity of the isocyanate compound with respect to the carboxyl group is very small as compared with the reactivity of the same isocyanate compound with respect to the alcoholic hydroxyl group,
The ethylenically unsaturated bond is mainly introduced in the portion of the alcoholic hydroxyl group-containing unit, and the ethylenically unsaturated bond introduced in the portion of the carboxyl group-containing unit is generally very small. Therefore, most of the carboxyl groups remain and alkali solubility is not lost.

When the curable resin thus obtained is used for forming a colored layer of a color filter, a protective film for covering the colored layer, or a columnar spacer for maintaining a cell gap of a liquid crystal panel, , GPC
The polystyrene reduced weight average molecular weight measured by (gel permeation chromatography) is 3,000 to 1,
, 000,000, preferably 5,000 to 1,000,0
00, more preferably in the range of 5,000 to 100,000. Weight average molecular weight is 30,
If it is less than 00, the alkali solubility is too high and it is difficult to control the pattern shape at the time of pattern exposure, and even when the pattern can be produced, there is a problem that the final film thickness is reduced (film reduction). On the other hand, the weight average molecular weight is 1,000,000.
If it is greater than 0, there is a problem that the viscosity becomes too high when it is made into a resist, the coating suitability deteriorates, the developability deteriorates, and it becomes difficult to remove the pattern.

The acid value of the curable resin is 5 mgKOH / g to 4
00 mgKOH / g, preferably 10 mgKOH / g
It is preferable to be set to ˜200 mgKOH / g. The acid value is related to the alkali solubility, and if the acid value is too low, there are problems such as poor developability or poor adhesion to the substrate and the color filter resin. On the other hand, if the acid value is too high, there is a problem that the alkali solubility is too high and it is difficult to control the pattern shape during pattern exposure. The hydroxyl value of the curable resin is 5 mgKOH / g to 400 mgKOH
It can be adjusted in the range of / g.

The curable resin of the present invention is capable of appropriately controlling the curability of photocuring reaction, alkali solubility, coating property, etc., has high sensitivity to exposure, and is excellent in heat resistance and chemical resistance after curing. Therefore, it can be suitably used as an active ingredient of a photocurable coating material, and in particular, for forming a convex layer for maintaining a colored layer of a color filter, a protective film or a cell gap of a liquid crystal panel. Are suitable.

If necessary, the curable resin for forming a photosensitive pattern according to the present invention has a photopolymerizable compound (polyfunctional polymerizable compound) having two or more photopolymerizable functional groups, a photopolymerization initiator, By adding a sensitizer or the like, a curable resin composition suitable as a photocurable coating material can be obtained.

In the present invention, the curable resin composition for forming a photosensitive pattern is contained in the curable resin for forming a photosensitive pattern in a solid content ratio (that is, a ratio based on the total solid content).
And usually 5 to 80% by weight, preferably 10 to 50% by weight
Include. 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 curable resin exceeds 80% by weight, the viscosity of the coating liquid becomes too high, the fluidity is lowered, and the coating property is deteriorated. On the other hand, the content of curable resin is 5% by weight
If it is less than the above range, the viscosity of the coating solution becomes too low, and as a result, the stability of the coating film after coating and drying becomes insufficient, and problems such as impairing exposure and developing suitability may occur.

When a spacer is formed using the above-mentioned curable resin composition for forming a photosensitive pattern, if the content of the curable resin exceeds 80% by weight, the viscosity of the coating liquid becomes too high and the fluidity becomes poor. As a result, it becomes difficult to form a uniform fine spacer, which causes unevenness in the gap during cell assembly, which is not preferable. Also,
In this case, if the content of the curable resin is less than 5% by weight, the elastic deformation rate of the pattern formed by performing exposure and development using the curable resin composition will be small, and the elastic modulus will be large in a wide temperature range. It becomes difficult to form a pattern having a deformation rate and a small plastic deformation rate. Here, the elastic deformation rate (%) and the plastic deformation rate (%) are calculated by the following equations, respectively. Formula of elastic deformation rate: [(elastic deformation amount / total deformation amount) × 10
0] (%) Formula of plastic deformation rate: [(plastic deformation amount (T2) / total deformation amount (T1)) x 100] (%) The polyfunctional photopolymerizable compound itself undergoes a polymerization reaction by light irradiation. A compound that initiates or initiates a polymerization reaction by the action of active species such as a photopolymerization initiator activated by light irradiation, and is a component that improves the crosslink density of the curable resin composition.

In the present invention, as the polyfunctional photopolymerizable compound (polyfunctional polymerizable compound), a photopolymerizable compound having two or more, preferably three or more, photopolymerizable functional groups in one molecule is used. The reaction type of the polyfunctional photopolymerizable compound is not limited, and may be any of photoradical polymerization, photocationic polymerization, and photoanionic polymerization. The photoradical polymerizable compound is a cyclic imide group represented by Formula 1. Both are preferable because they can be photopolymerized, and a compound having two or more ethylenically unsaturated bonds in one molecule is particularly preferable. The polyfunctional photopolymerizable compound may be a monomer, an oligomer, or a polymer having a relatively large molecular weight, but in order to sufficiently improve the crosslinking density with a relatively small amount, it is preferable to use the monomer or oligomer. preferable.

As the compound having two or more ethylenically unsaturated bonds in one molecule, a polyfunctional acrylate monomer or oligomer is preferably used, and examples thereof include ethylene glycol (meth) 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, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, 1,4-butanediol diacrylate, penta Examples thereof include erythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. You may use these components in combination of 2 or more types.

The polyfunctional polymerizable compound preferably contains a monomer having three or more ethylenically unsaturated bonds, and the content thereof is about 30 to 95% by weight based on the amount of the polyfunctional polymerizable compound used. It is preferable to occupy.

The polyfunctional polymerizable compound preferably has an alcoholic hydroxyl group together with two or more ethylenically unsaturated bonds. When the polyfunctional polymerizable compound has an alcoholic hydroxyl group, when photocuring the curable resin composition, the hydrogen abstraction effect to the alcoholic hydroxyl group-containing polyfunctional polymerizable compound of the cyclic imide group, the curable resin of The reactivity and the curability can be improved by increasing the reactivity of the polyfunctional polymerizable compound containing a cyclic imide group and an alcoholic hydroxyl group.

Specific examples of the polyfunctional polymerizable compound having an alcoholic hydroxyl group include 2-hydroxy-1-
(Meth) acryloxy-3- (meth) acryloxypropane, pentaerythritol di (meth) acrylate monostearate, tetramethylolmethane tri (meth)
Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, epichlorohydrin-modified bisphenol A di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate,
Examples thereof include epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate and triglycerol di (meth) acrylate.

Further, these polyfunctional polymerizable compounds include
As a reaction diluent, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, etc. Can be added.

The content of the polyfunctional polymerizable compound is usually 3 to 50% by weight, preferably 5 to 40% by weight in terms of solid content in the curable resin composition, but in the case of forming a spacer. , Usually 3 to 90 to obtain sufficient elastic deformation rate
%, Preferably 5 to 85% by weight. If the polyfunctional polymerizable compound is too small, the adhesive strength of the coating film formed,
The inconvenience that various physical strengths such as heat resistance become insufficient occurs, and when the amount of the polyfunctional polymerizable compound is too large, the stability of the curable resin composition is decreased and the coating film formed is easily formed. The inconvenience of insufficient flexibility occurs. Further, this ratio is also necessary to improve the dissolution property in the developing solution, and when it is out of the range of the optimized amount, the pattern is resolved but the monomer curing speed increases,
Scum and whiskers occur around the pattern. Further, outside the above range, in a severe case, resist reattachment due to partial swelling / peeling may occur, which may hinder accurate pattern formation.

Examples of the photopolymerization initiator include ultraviolet rays, ionizing radiation, visible light, and other wavelengths, especially 365 μm.
The photoradical polymerization initiator which can be activated by the following energy rays can be used. Since the cyclic imide group represented by Formula 1 has radical polymerization reactivity, a polyfunctional photopolymerizable compound having radical polymerization reactivity is also used, and the photopolymerization initiator is mainly a photopolymerization initiator. Although a radical polymerization initiator is used, when the polyfunctional polymerizable compound is a polymerization reaction system other than radical polymerization, a compound suitable for the reaction system may be used.

The photoradical polymerization initiator is, for example, a compound which generates a free radical by the energy of ultraviolet rays, and is a benzophenone derivative such as benzoin and benzophenone or a derivative thereof such as an ester; xanthone and thioxanthone derivative; chlorosulfonyl,
Chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, halogen-containing compounds such as chloromethylbenzophenones; triazines; fluorenones; haloalkanes; redox couples of photoreducible dyes and reducing agents; organic sulfur compounds; There are peroxides. Preferably, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907, Darocurure 1173 (all manufactured by Ciba Specialty Chemicals), Adeka 1717 (manufactured by Asahi Denka Co., Ltd.), 2, 2'- Bis (o-chlorophenyl) -4,
Examples thereof include ketone-based and biimidazole-based compounds such as 5,4′-tetraphenyl-1,2′-biimidazole (manufactured by Kurogane Chemical Co., Ltd.). These initiators can be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable not to disturb the absorption spectral characteristics.

The photopolymerization initiator is contained in the curable resin composition in a solid content ratio of usually 0.05 to 18% by weight, preferably 0.1 to 13% by weight. If the addition amount of the photopolymerization initiator is less than 0.05% by weight, the photocuring reaction does not proceed,
The residual film rate, heat resistance, chemical resistance, etc. tend to decrease.
If the amount added exceeds 18% by weight, the solubility in the base resin reaches saturation and crystals of the initiator precipitate during spin coating or coating leveling, making it impossible to maintain the homogeneity of the film surface. A problem called occurrence of film roughness occurs.

When preparing the curable resin composition, the photopolymerization initiator may be added to the curable resin for forming the photosensitive pattern from the beginning, but when it is stored for a relatively long period of time. Is preferably dispersed or dissolved in the curable resin composition immediately before use.

A sensitizer may be added when it is desired to improve the photosensitivity. The sensitizer used is preferably a styryl compound or a coumarin compound. Specifically, 2- (p-dimethylaminostyryl) quinoline, 2
-(P-diethylaminostyryl) quinoline, 4- (p
-Dimethylaminostyryl) quinoline, 4- (p-diethylaminostyryl) quinoline, 2- (p-dimethylaminostyryl) -3,3-3H-indole, 2- (p
-Diethylaminostyryl) -3,3-3H-indole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-diethylaminostyryl) -benzoxazole, 2- (p-dimethylaminostyryl) benzimidazole, 2 Examples thereof include-(p-diethylaminostyryl) -benzimidazole.

The coumarin compounds include 7-diethylamino-4-methylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 4,6-diethylamino-7-ethylaminocoumarin, and 3- (2-benz). Imidazolyl) -7-N, N-diethylaminocoumarin, 7-diethylaminocyclopenta (c) coumarin,
7-amino-4-trifluoromethylcoumarin, 1,
2,3,4,5,3H, 6H, 10H-tetrahydro-
8-trifluoromethyl (1) benzopyrano- (9,9
a, 1-gh) -Quinolidin-10-one, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 1,2,3,4,5,3H, 6H, 10H-tetrahydro-9-carbetoxy. (1) Benzopyrano- (9,
9a, 1-gh) -quinolizin-10-one and the like.

Further, in the curable resin composition for forming a photosensitive pattern of the present invention, if necessary, for the purpose of improving heat resistance, adhesion and chemical resistance (particularly alkali resistance),
A compound (epoxy resin) having two or more epoxy groups in the molecule can be blended. Examples of the compound having two or more epoxy groups in the molecule include Epicoat 1001, 100 as bisphenol A type epoxy resin.
2, 1003, 1004, 1007, 1009, 101
0 (manufactured by Japan Epoxy Resin), bisphenol F type epoxy resin such as Epicoat 807 (manufactured by Japan Epoxy Resin), phenol novolac type epoxy resin EPPN201, 202 (manufactured by Nippon Kayaku),
Epicoat 154 (made by Japan Epoxy Resin), etc.
EOCN1 as cresol novolac type epoxy resin
02, 103S, 104S, 1020, 1025, 10
27 (manufactured by Nippon Kayaku), Epicoat 180S (manufactured by Japan Epoxy Resin), and the like can be exemplified. Furthermore, a cycloaliphatic epoxy resin and an aliphatic polyglycidyl ether can also be illustrated.

Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable. Most of the compounds having two or more of these epoxy groups in the molecule are high molecular weight compounds,
The glycidyl ethers of bisphenol A and bisphenol F are low molecular weight substances, and such low molecular weight substances are particularly preferable. Further, an acrylic copolymer containing glycidyl (meth) acrylate, oxetane (meth) acrylate, alicyclic epoxy (meth) acrylate or the like in the resin skeleton is also effective.

Such an epoxy resin is contained in the curable resin composition in a solid content ratio of usually 0 to 60% by weight, preferably 5 to 40% by weight. When the content of the epoxy resin is less than 5% by weight, the protective film may not have sufficient alkali resistance. On the other hand, the epoxy resin content is 6
If it exceeds 0% by weight, the amount of epoxy resin becomes too large,
It is not preferable because the curable resin composition has poor storage stability and developability. The epoxy resin is also effective for removing tack in the dry coating film of the curable resin composition, and a sufficient effect is exhibited when the addition amount is about 3% by weight. The epoxy resin reacts with the acidic groups remaining in the coating film without reacting even after exposure and alkali development by heat treatment, and imparts excellent alkali resistance to the coating film.

In addition to the above-mentioned components, various additives such as a surfactant and a silane coupling agent may be added to the above-mentioned curable resin composition, if necessary.

Further, when the colored layer of a color filter is formed using the curable resin composition for forming a photosensitive pattern of the present invention, a colorant such as a pigment or a dye is added to the curable resin composition. To do. As the coloring agent, R of the coloring layer,
According to the desired color of G, B, etc., select and use fine particles that are heat resistant to withstand the heating process of the color filter and that can be dispersed well, from organic and inorganic colorants. You can

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. Further, specific examples of the inorganic pigment or extender pigment, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, Dark blue,
Examples include chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. In the present invention, the coloring materials may be used alone or in combination of two or more.

The colorant is added to the curable resin composition for forming a photosensitive pattern of the present invention in an amount of usually 40 to 75% by weight, preferably 45 to 70% by weight. When the blending ratio of the colorant is less than the above range, the coloring power of each colored layer is insufficient, and it is difficult to display a clear image. On the other hand, when it exceeds the above range, the light transmittance of each colored layer is low. It causes inconvenience such as insufficient.

When a colorant is added to the curable resin composition, a dispersant may be added to the curable resin composition in order to uniformly and stably disperse the colorant. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants, etc. can be used. Among the surfactants, the following polymer surfactants (polymer dispersants) are preferable.

That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkyl such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether. Polymer surfactants such as phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes are preferably used.

The curable resin composition for forming a photosensitive pattern of the present invention is usually dissolved in an imide group-containing copolymer, a polyfunctional polymerizable compound, a photopolymerization initiator, etc. in consideration of coating and coating suitability. A solvent having a relatively high boiling point is contained so as to have good properties and good spin coating properties. Examples of usable solvents include methyl alcohol, ethyl alcohol, N-propyl alcohol, i-
Alcohol solvents such as propyl alcohol; cellosolve solvents such as methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxy ethoxy ethanol and ethoxy ethoxy ethanol; ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, lactic acid Ester-based solvents such as ethyl; ketone-based solvents such as acetone, methyl isobutyl ketone, cyclohexanone; cellosolve acetate-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Tall acetate solvent: diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether Le, ether solvents such as tetrahydrofuran; N, N-dimethylformamide, N, N-
Aprotic amide solvents such as dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; N-heptane, N-hexane, N- An organic solvent such as a saturated hydrocarbon solvent such as octane can be exemplified. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; methoxyethoxyethyl acetate,
Carbitol acetate solvents such as ethoxyethoxyethyl acetate; ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol diethyl ether;
Ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are particularly preferably used. Particularly preferably, MBA (-3-methoxybutyl acetate, CH ₃ CH (OCH ₃ ) CH ₂ CH ₂ OCOCH
₃ ), PGMEA (propylene glycol monomethyl ether acetate, CH ₃ OCH ₂ CH (CH ₃ ) OCO
CH ₃ ), DMDG (diethylene glycol dimethyl ether, H ₃ COC ₂ H ₄ OCH ₃ ) or a mixture thereof can be used, and these are used to adjust the solid content concentration to 5 to 50% by weight.

In order to produce the curable resin composition for forming a photosensitive pattern of the present invention, the curable resin, the polyfunctional polymerizable compound, the photopolymerization initiator, and other components are added to an appropriate solvent. It may be dissolved and dispersed by a general method such as a paint shaker, a bead mill, a sand grind mill, a ball mill, an attritor mill, a two roll mill, or a three roll mill. As the main polymer curable resin, the one obtained by isolating and purifying the imide group-containing copolymer which is the active ingredient after the synthesis reaction is used, and the reaction solution obtained by the synthesis reaction, its dried product, etc. are used as they are. You may use.

When the curable resin composition thus obtained is applied to a support to form a coating film, and the coating film is irradiated with activation energy rays such as ultraviolet rays and ionizing radiation, the imide group-containing compound Photopolymerizable functional groups and cyclic imide groups of polymers, and polyfunctional polymerizable compounds such as bifunctional or higher functional acrylic monomers cause photoradical polymerization reaction and also cause dimerization reaction between cyclic imide groups. By this, a cross-linking bond is formed between the molecules of the imide group-containing copolymer, and the copolymer is cured.

In particular, when the photopolymerizable group-containing unit of the imide group-containing copolymer or the polyfunctional photopolymerizable compound has photoradical polymerizability such as an ethylenically unsaturated bond, the cyclic imide group and these Since a cross-linking bond is also formed between the structural unit and the compound, it contributes to the improvement of physical properties after curing, and is excellent in terms of elastic deformation rate, total deformation rate, hardness, strength heat resistance, and adhesion. Physical properties are easily obtained.

In this curable resin composition, the photopolymerizable functional group and the cyclic imide group coexist as crosslinkable functional groups in the molecule of the imide group-containing copolymer as the main polymer, and the reaction of the cyclic imide group occurs. The high reactivity and the high reaction point density of the cross-linking reaction make the exposure sensitivity very high even with a small amount of photopolymerization initiator, and with a small exposure amount, or
It can be cured with a very short exposure time. Therefore, the curing time can be shortened, and the energy for exposure and the amount of the photopolymerization initiator used can be saved.

In addition, since the amount of the photopolymerization initiator used is small, the heat discoloration resistance after curing is excellent, and particularly when used as a protective film of a color filter or a coloring layer, yellowing hardly occurs due to a heating process, and transparency is improved. Is excellent. Furthermore, this curable resin composition has various physical properties such as coating strength, heat resistance, and chemical resistance after curing due to the presence of cyclic imide groups in the crosslinking reaction and the high reaction point density of the crosslinking reaction. Is also excellent.

Further, when an alcoholic hydroxyl group is contained in the molecule of the imide group-containing copolymer or polyfunctional polymerizable compound, the hydrogen abstraction effect of the imide group to the alcoholic hydroxyl group-containing methylene group or methine group is obtained. As a result, radicals are generated, so that the reactivity of the crosslinking reaction is further increased, and the exposure sensitivity and curability are improved.

In the present invention, the exposure sensitivity of the curable resin composition can be evaluated by the following method. First, a curable resin composition is applied onto a substrate and dried as necessary to form a coating film. Here, as the substrate, a transparent glass substrate that does not interfere with a series of pattern forming steps such as exposure and development can be used without any particular problem. Although the thickness of the coating film is not particularly limited, it is usually about 1 to 10 μm. This coating film is applied under appropriate conditions, for example, at 70 to 150 ° C. for 1 to 10 minutes,
Pre-bake. After prebaking, the coating film is exposed with a known irradiation intensity and the film thickness is measured. The film thickness measured at this stage is referred to as "pre-development film thickness".

Next, the pre-baked coating film is brought into contact with a suitable developer to dissolve and remove the unexposed portion, and the remaining exposed portion is washed as necessary to develop the coating film.
Here, the composition of the developer and the developing conditions are appropriately selected according to the curable resin composition to be tested. It is needless to say that the developer is preferably one that hardly dissolves the exposed portion (cured portion) of the curable resin composition and completely dissolves the unexposed portion. Then, the developed coating film is subjected to appropriate conditions, for example, at 180 to 280 ° C. for 20 to 20 ° C.
Post bake for 80 minutes. After post-baking, the thickness of the coating film is measured, and the result is referred to as the "film thickness after final curing".

From the film thickness before development and the film thickness after final curing thus measured, the residual film ratio is calculated according to the following equation.

Residual film rate (%) = (film thickness after final curing (μm)
÷ Pre-development film thickness (μm)) × 100 On the other hand, the same curable resin composition is applied onto the substrate in the same manner as above, dried and prebaked to form a reference coating film. The coating film for reference is exposed with an irradiation intensity at which the coating film is completely cured, and the film thickness is measured. The film thickness measured at this stage is referred to as "complete exposure film thickness". next,
The post-baking was performed in the same manner as the sample without developing the completely exposed coating film, and then the film thickness of the obtained film was measured by the same method as described above, and the "final film thickness without developing step" was given. To do. Then, the reference residual film rate is calculated from the measured completely exposed film thickness and the final film thickness without the developing step according to the following equation.

Reference residual film rate (%) = (final film thickness without development step (μm) ÷ complete exposure film thickness (μm)) × 10
0 In this way, the residual film rate and the reference residual film rate are calculated,
The smallest exposure amount at which the residual film ratio is equal to the reference residual film ratio with the error range of 1% is determined as the minimum exposure amount of the curable resin composition. It can be evaluated that the smaller the minimum exposure amount, the higher the sensitivity.

According to the present invention, the minimum exposure dose thus determined is 100 mJ / cm ² or less, preferably 5
0 mJ / cm ² or less, more preferably 35 mJ / cm ²
Hereafter, it is possible to obtain a curable resin composition having a very high sensitivity, which is more preferably 25 mJ / cm ² or less.

The curable resin composition for forming a photosensitive pattern of the present invention comprises a colored layer for a color filter, a protective layer for covering the colored layer, and a convex spacer for maintaining the cell gap of the liquid crystal panel substrate. It is particularly suitable for forming a negative permanent film in a wide range of fields such as a flattening film of a TFT array substrate or an interlayer insulating film for semiconductor devices. it can.

The color filter according to the present invention comprises a transparent substrate and a colored layer formed on the transparent substrate, and is provided on a protective film covering the colored layer and / or a non-display area of the substrate. A spacer may be provided, and at least one of the colored layer, the protective film and the spacer is formed by curing the curable resin composition for forming a photosensitive pattern according to the present invention. Is characterized by.

Moreover, the liquid crystal panel substrate according to the present invention is
By providing multiple spacers in the non-display area on the substrate,
The spacer is formed by curing the resin composition according to the present invention, and is 2.0 GPa at room temperature.
The elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] is 60% or more with respect to the compressive load.
The liquid crystal panel substrate provided with such a spacer may be the color filter as the display side substrate or the liquid crystal driving side substrate.

FIG. 3 shows an example of the 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.

This color filter 103 comprises a black matrix 6 formed in a predetermined pattern on the transparent substrate 5, a coloring layer 7 (7R, 7G, 7B) formed in a predetermined pattern on the black matrix, and the coloring. The protective film 8 is formed so as to cover the layers. 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 spacer 12 is one shape of a convex spacer, and a plurality of predetermined positions (five in FIG. 3) on the transparent electrode 9 in accordance with the region (non-display region) where the black matrix layer 6 is formed. Is formed in. The columnar spacer 12 is formed on the transparent electrode 9, the colored layer 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 and are transparent so as to cover them. You may form the layer of an electrode. Further, when the color filter does not include the black matrix layer, columnar spacers can be formed in the region where the colored layer 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 composed of the colored layers 7R, 7G, and 7C in order to improve the contrast of the displayed image.
It is provided so as to surround the area between 7B and the outside of the colored layer 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 curable resin composition containing light-shielding particles.

In the method using a photosensitive resist,
First, a metal thin film of chromium or the like is formed on the transparent substrate 5 as a light shielding layer by a vapor phase growth method such as a sputtering method or a vacuum deposition method, or carbon black is formed on a resin such as a polyimide resin, an acrylic resin or an epoxy resin. A resin layer made of a resin composition containing light-shielding particles such as 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, the black matrix layer 6 can be formed by etching the light-shielding layer in the portion exposed by development and removing the remaining photosensitive resist.

In the method using the curable resin composition containing the light-shielding particles, first, on the transparent substrate 5,
A curable resin composition containing light-shielding particles such as carbon black or metal oxide is applied, and dried as necessary to form a photosensitive coating film, and the coating film is used as a photomask for a black matrix. The black matrix layer 6 can be formed by exposing and developing via the above, and subjecting to heat treatment as necessary. The curable resin composition according to the present invention may be used as the curable resin composition mixed with the light shielding particles.

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 colored layer 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 coloring layer 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, pigment dispersion using a curable resin composition containing a coloring agent such as a pigment. It is preferably formed by a method.

In the case of the pigment dispersion method, first, a colorant such as a pigment is dispersed in the curable resin composition to prepare red, green and blue photocurable colored resin compositions, respectively. To do. 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 colored layer 7R is formed by performing exposure through a red pattern photomask, alkali development, and then heat curing in a clean oven or the like.
After that, each color is patterned in the same manner using the photocurable colored resin compositions for green and blue in order to form the green colored layer 7G and the blue colored layer 7B.

As the colorant, the above-mentioned colorants can be appropriately selected and used. The curable resin composition according to the present invention is preferably used as the curable resin composition mixed with the colorant.

The thickness of the coloring layer is usually 0.5 to 2.5 μm.
The degree. In addition, even if the red colored layer 7R is the thinnest, the green colored layer 7G and the blue colored layer 7B are thicker in this order, the thickness of the colored layers of each color is changed to set the optimum liquid crystal layer thickness 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 colored layer 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 coloring layer 7. It can be formed by curing with light or heat. As the photocurable transparent resin composition for forming the protective film, the curable resin composition according to the present invention is preferably used.

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.

The convex spacer is the color filter 10
In order to maintain the cell gap when the liquid crystal driving side substrate such as 3 is bonded to the liquid crystal driving side substrate such as the TFT array substrate, a plurality of them are provided in the non-display area on the substrate. The shape and size of the convex spacer can be selectively provided in the non-display area on the substrate,
There is no particular limitation as long as a predetermined cell gap can be maintained over the entire substrate. When the columnar spacer 12 as shown in the figure is formed as a convex spacer, it has a constant height in the range of about 2 to 10 μm, and the protruding height (pattern thickness) is required for the liquid crystal layer. It can be appropriately set based on the thickness and the like. Further, the thickness of the columnar spacer 12 can be appropriately set within the range of about 5 to 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 columnar,
For example, a cylindrical shape, a prismatic shape, a truncated cone shape, or the like may be used.

The convex spacer of the liquid crystal panel substrate according to the present invention represented by the color filter 103 is obtained by reacting and curing the resin composition according to the present invention as a binder polymer, and is compressed to 2.0 GPa at room temperature. Elastic deformation rate [(elastic deformation amount / total deformation amount) x 1 against load
00] is 60% or more, 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 convex spacer can be measured by the following method. As a device that measures the amount of deformation by applying a load to the convex 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. 5 shows the behavior of the convex spacer in the process of compressing the convex spacer of height T and releasing the load by using such a device, the total deformation amount (T1), the plastic deformation amount (T2) and Elastic deformation (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 convex spacer by using the above-mentioned device to push the indenter, thereby increasing the height of the convex spacer. 22m in the thickness direction (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 convex spacer is measured. Next, by raising the indenter pressed against the convex 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 at room temperature of the convex spacer is 6
If it is less than 0%, it tends to be plastically deformed at room temperature,
The function of the spacer, which maintains an accurate and uniform cell gap, cannot be fully 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 easily causes bubbles.

In the present invention, the convex 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 driving side substrate may come into contact with each other during cell pressure bonding, and the color filter or the liquid crystal driving side substrate may be damaged, resulting in uneven display.

The convex spacer satisfying the above physical properties is
It can be formed using the curable resin composition according to the present invention. That is, first, the coating liquid of the curable resin composition according to the present invention is applied directly on a transparent substrate by a method such as spin coater, roll coater, spraying, or printing, or through another layer such as a transparent electrode. Then, it is dried to form a photocurable resin layer. The rotation speed of the spin coater may be set within the range of 500 to 1500 rotations / minute as in the case of forming the protective film. Next, this resin layer is exposed through a photomask for a convex spacer and is developed with a developing solution such as an alkaline solution to form a predetermined convex pattern, and this convex pattern is cleaned in a clean oven if necessary. The convex spacers are formed by heat treatment (post-baking) with the like.

The convex 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 convex spacer may be formed thereon, or a protective film and a transparent electrode may be formed on the color filter in this order, and a transparent electrode may be further formed. A convex spacer may be formed on the top.

The orientation film 10 is provided on the inner surface side of the color filter so as to cover the display portion including the colored layer 7 and the non-display portion including the black matrix layer 6 and the columnar spacers 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 driving side substrate) are opposed to each other and the inner peripheral edge portions of both substrates are joined by 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.

The ODF (One Drop Fill) method is a method in which liquid crystal is dropped on a substrate and then the opposing substrates are bonded at once with a predetermined cell gap left therebetween. Due to problems such as non-uniformity, insufficient adhesive strength of sealing material, and liquid crystal contamination, it has been difficult to achieve industrial application.
Considering the situation such as development of convex spacers, improvement of their reliability, and development of photo-curing sealing material with good adhesiveness, application to industrial manufacturing has come to be expected. Since the convex 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 spacers that are elastically deformed appropriately with respect to the compressive load at room temperature, when the bonding is carried out by the room temperature cell pressure bonding method, the uneven pressure is alleviated. Alternatively, by 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 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.

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 type driving substrate. When applied to a liquid crystal drive side substrate such as a TFT array substrate, the spacer on the liquid crystal drive side substrate is provided in a region (non-display region) overlapping the black matrix layer of the display side substrate to be combined.

[0210]

EXAMPLES Example 1 (1) Synthesis of Copolymer Resin Solution 1 80 parts by weight of 3,4,5,6 tetrahydrophthalimidoethyl methacrylate (THPI-MA) in a polymerization tank,
20 parts by weight of methacrylic acid (MAA), 185 parts by weight of diethylene glycol dimethyl ether (DMDG),
After charging, stirring and dissolving, 2,2'-azobis (2
-Methylbutyronitrile) was added in an amount of 4 parts by weight and uniformly 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. Further, 10 g of glycidyl methacrylate (GMA) was added to the obtained solution.
Parts by weight, 0.5 parts by weight of triethylamine, and 0.1 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 35%).
Got

(2) Preparation of curable resin composition 1 The following amounts of the following materials were stirred and mixed at room temperature to obtain curable resin composition 1.

<Composition of Curable Resin Composition 1> Copolymer resin solution 1 (solid content 35%): 69.0 parts by weight Dipentaerythritol pentaacrylate (SR399, Sartomer Co.): 11.0 parts by weight・ Orthocresol novolac type epoxy resin (Japan Epoxy Resin, Epicoat 180S70): 1
5.0 parts by weight 2-methyl-1- (4-methylthiophenyl) -2-
Morpholinopropanone-1: 1.5 parts by weight 2,2'-bis (O-chlorophenyl) -4,5,
4 ′, 5′-tetraphenyl-1,2′-biimidazole: 1.0 part by weight Diethylene glycol dimethyl ether: 66.0 parts by weight (Example 2) (1) Synthesis of copolymer resin solution 2 In a polymerization tank. 80 parts by weight of THPI-MA and 15 parts of MAA
Parts by weight, 2-hydroxyethyl methacrylate (HEM
5 parts by weight of A) and 185 parts by weight of DMDG were charged, stirred and dissolved, and then 4 parts by weight of 2,2′-azobis (2-methylbutyronitrile) was added and uniformly 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. Furthermore, 10 parts by weight of GMA, 0.5 parts by weight of triethylamine, and 0.1 parts by weight of hydroquinone were added to the resulting solution, and 1
Stir at 00 ° C for 5 hours to obtain the target copolymer resin solution 2
(Solid content 38%) was obtained.

(2) Preparation of curable resin composition 2 A composition was prepared in the same manner as in Example 1 except that the resin used was changed to the copolymer resin solution 2 to obtain a curable resin composition 2. .

Example 3 (1) Synthesis of Copolymer Resin Solution 3 80 parts by weight of THPI-MA and 10 parts of MAA were placed in a polymerization tank.
1 part by weight, 10 parts by weight of HEMA, and 185 parts by weight of DMDG were charged, stirred and dissolved, and then 4 parts by weight of 2,2′-azobis (2-methylbutyronitrile) was added and uniformly dissolved. It was Then, the mixture was stirred at 85 ° C. for 2 hours under a nitrogen stream and further reacted at 100 ° C. for 1 hour. Furthermore, 10 parts by weight of methacryloyloxyethyl isocyanate (MOI), 0.1 parts by weight of dibutyltin laurate, and 0.1 parts by weight of hydroquinone were added to the obtained solution, and the mixture was stirred at 60 ° C. for 3 hours to obtain the purpose. To obtain a copolymer resin solution 3 (solid content: 38%).

(2) Preparation of curable resin composition 3 A composition was prepared in the same manner as in Example 1 except that the resin used was changed to the copolymer resin solution 3 to obtain a curable resin composition 3. .

Comparative Example 1 (1) Synthesis of Copolymer Resin Solution 4 80 parts by weight of THPI-MA and 20 parts of MAA were placed in a polymerization tank.
By weight, 185 parts by weight of DMDG were charged, stirred and dissolved, and then 4 parts by weight of 2,2′-azobis (2-methylbutyronitrile) was added and uniformly dissolved. Then, the mixture was stirred under a nitrogen stream at 85 ° C. for 2 hours, and further stirred for 10
React at 0 ° C. for 1 hour to obtain the target copolymer resin solution 4
(Solid content 35%) was obtained.

(2) Preparation of curable resin composition 4 A composition was prepared in the same manner as in Example 1 except that the resin used was changed to the copolymer resin solution 4 to obtain a curable resin composition 4. .

Example 4 (1) Synthesis of Copolymer Resin Solution 5 Tetrahydrophthalimide acrylate (T
HPI-A) 75 parts by weight, acrylic acid (AA) 25
Parts by weight, diethylene glycol dimethyl ether (DM
185 parts by weight of DG) was added, and the mixture was stirred and dissolved,
2,2'-azobis (2-methylbutyronitrile) was added to 4
Part by weight was added and uniformly 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. Furthermore, 15 parts by weight of glycidyl methacrylate (GMA) and triethylamine of 0.
8 parts by weight and 0.2 parts by weight of hydroquinone were added and stirred at 100 ° C. for 5 hours to obtain a target copolymer resin solution 1 (solid content 39%). The physical properties of the obtained copolymer are shown in Table 1.

(2) Preparation of curable resin composition 5 The following amounts of the following materials were stirred and mixed at room temperature to obtain curable resin composition 5.

<Composition of the curable resin composition 5> The above copolymer resin solution 5 (solid content 39%): 41 parts by weight Dipentaerythritol pentaacrylate (Sartomer SR399): 16 parts by weight Orthocresol Novolac Type epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 180S7)
0): 4 parts by weight 2-methyl-1- (4-methylthiophenyl) -2-
Morpholinopropan-1-one: 4 parts by weight Diethylene glycol dimethyl ether: 35 parts by weight (Example 5) (Preparation of curable resin composition 6) The following materials in the following amounts were stirred and mixed at room temperature to prepare a curable resin composition. Item 6 was obtained.

<Composition of curable resin composition 6> -Copolymer resin solution 5 (solid content 39%): 10 parts by weight-Dipentaerythritol pentaacrylate (SR 399, SR399): 28 parts by weight-Orthocresol novolak Type epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 180S7)
0): 4 parts by weight 2-methyl-1- (4-methylthiophenyl) -2-
Morpholinopropan-1-one: 4 parts by weight Diethylene glycol dimethyl ether: 54 parts by weight (Comparative Example 2) (1) Synthesis of copolymer resin solution 6 75 parts by weight of methyl methacrylate (MMA) and acrylic acid in a polymerization tank. 25 parts by weight of (AA) and 185 parts by weight of diethylene glycol dimethyl ether (DMDG) were charged, stirred and dissolved, and then 2,2′-azobis (2-
4 parts by weight of (methyl butyronitrile) was added and uniformly 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. Further, 15 parts by weight of glycidyl methacrylate (GMA), 0.8 parts by weight of triethylamine, and 0.2 parts by weight of hydroquinone were added to the obtained solution, and the mixture was stirred at 100 ° C. for 5 hours to obtain the objective. Copolymer resin solution 6 (solid content 39%) was obtained. The physical properties of the obtained copolymer are shown in Table 1.

(2) Preparation of curable resin composition 7 A curable resin composition 7 was obtained by preparing a composition in the same manner as in Example 4 except that the resin used was a curable resin solution 6. .

[0223]

[Table 1]

Example 6 (1) Formation of Black Matrix First, the respective components in the following amounts were mixed and sufficiently dispersed in a sand mill to prepare a black pigment dispersion liquid.

<Composition of Black Pigment Dispersion Liquid> Black pigment: 23 parts Polymer dispersant (manufactured by Big Chemie Japan Ltd. Di
sperbyk 111): 2 parts by weight Solvent (diethylene glycol dimethyl ether): 7
5 parts by weight Next, the following components were thoroughly mixed to obtain a light-shielding layer composition.

<Composition of composition for light-shielding layer> -Black pigment dispersion: 61 parts by weight-Curable resin composition of Example 1 1:20 parts by weight-Diethylene glycol dimethyl ether: 30 parts by weight and thickness 1. The composition for a light-shielding layer was applied onto a 1 mm glass substrate (AL material manufactured by Asahi Glass Co., Ltd.) by a spin coater and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. The light-shielding layer is exposed to a light-shielding pattern with an ultra-high pressure mercury lamp and then developed with a 0.05% potassium hydroxide aqueous solution, and then the substrate is exposed to an atmosphere of 180 ° C. for 30 minutes.
By leaving it for a minute, heat treatment was performed to form a black matrix in the region where the light-shielding portion was to 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 is arranged 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 is used by a proximity liner to form only a region corresponding to a region where a colored layer is formed. 1 ultraviolet ray
Irradiate for 0 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. After that, the substrate was left in an atmosphere of 180 ° C. for 30 minutes for heat treatment to form a red relief pattern in a region where a red pixel should 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 an area where a blue pixel is to be formed, in the same step 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.

<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 of Example 1: 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight <green curable resin Composition of composition> -C. I. Pigment Green 36:10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, curable resin composition of Example 1: 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight <blue curable resin Composition of composition> -C. I. Pigment Blue 15: 6: 10 parts by weight-Polysulfonic acid type polymer dispersant: 3 parts by weight-Curable resin composition of Example 1 1: 5 parts by weight-3-methoxybutyl acetate: 82 parts by weight (Example 7 ) A black matrix and a colored layer were formed in the same manner as in Example 6 except that the curable resin composition 5 obtained in Example 4 was used instead of the curable resin composition.

(Example 8: Formation of protective film) [0232] The curable resin composition 1 of Example 1 was applied onto the glass substrate having the colored layer formed in Example 6 by a spin coating method and dried to obtain a dry film thickness. A 2 μm coating film was formed.

100 μm from the coating film of the curable resin composition 1
A photomask was placed at a distance of 2 mm, and an ultraviolet ray was irradiated for 10 seconds only to a region corresponding to a colored layer forming region by using a 2.0 kW ultra-high pressure mercury lamp with a proximity liner. Then, it was dipped 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 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.

(Example 9: Formation of Protective Film) The glass substrate on which the colored layer was formed in Example 7 was used, and the curable resin composition was added to the curable resin composition 5 obtained in Example 4.
The protective film was formed in the same manner as in Example 8 except that the above was changed to.

(Example 10: Formation of Spacer) Example 1 was formed on the glass substrate on which the colored layer was formed in Example 6.
The curable resin composition 1 obtained in 1 above was applied by a 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 10 mm, 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. Then, it was dipped 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 curable resin composition. Then, the substrate is placed in an atmosphere of 200 ° C. for 30 minutes.
The color filter of the present invention was obtained by performing a heat treatment by leaving it for a minute to form a fixed spacer.

Example 11: Formation of Spacer The glass substrate was changed to the glass substrate on which the protective film was formed in Example 9, and the curable resin composition was changed to the curable resin composition 5 obtained in Example 4. Except for the above, the same procedure as in Example 10 was carried out to form a fixed spacer having an upper end area of 100 μm ² and a thickness T of 4.5 μm to obtain a color filter of the present invention.

Example 12: Fabrication of Liquid Crystal Display Device The surface of the color filter obtained in Example 10 including fixed spacers was subjected to DC magnetron sputtering at a substrate temperature of 200 ° C. with argon and oxygen as discharge gas to form ITO. Was used as a target to form a transparent electrode film. After that, an alignment film made of polyimide was further formed on the transparent electrode film.

Next, the color filter and the TFT
The liquid crystal display device of the present invention, in which a glass substrate on which the above is formed is bonded using an epoxy resin as a sealing material under a pressure of 0.3 kg / cm ² at 150 ° C. to form a cell, and TN liquid crystal is sealed. Was produced.

Example 13 Production of Liquid Crystal Display Device The surface of the color filter obtained in Example 11 including the fixed spacers was subjected to DC magnetron sputtering at a substrate temperature of 200 ° C. using argon and oxygen as discharge gas to form ITO. Was used as a target to form a transparent electrode film. 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 overlaid, 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 14: Preparation of color filter)
Substrate temperature 2 on the colored layer of the glass substrate on which the colored layer was formed in Example 6 or on the protective film of the color filter on which the colored layer and the protective film were formed in Example 8.
A transparent electrode film was formed by using DC and magnetron sputtering method with ITO as a target, using argon and oxygen as discharge gas at 00 ° C. Then, an alignment film made of polyimide was further formed on the transparent electrode film to obtain a color filter.

(Example 15: Preparation of color filter) The curable resin composition 6 obtained in Example 5 was replaced with the curable resin composition 5 on the substrate on which the protective film was formed in Example 9. Using the same amount, a fixed spacer was formed in the same manner as in Example 11. That is, the black matrix, the colored layers of RGB colors and the protective film were formed using the curable resin composition 5, and the curable resin composition 6 was used only for the fixed spacers to form a color filter in the same manner as in Example 14. .

Example 16: Fabrication of Liquid Crystal Display Device Using the color filter obtained in Example 15, an alignment film was formed and cells were assembled in the same manner as in Example 13.
A liquid crystal display device of the present invention was produced.

(Comparative Example 3) Comparative Example 2 was carried out by substituting the curable resin composition 5 on the substrate on which the protective film was formed in Example 9.
Example 11 using the same amount of the curable resin composition 7 obtained in
A fixed spacer was formed in the same manner as in. That is, the black matrix, the colored layers of RGB colors, and the protective film were formed using the curable resin composition 5, and only the fixed spacers were formed using the curable resin composition 7.

(Comparative Example 4) Using the color filter obtained in Comparative Example 3, an alignment film was formed and cells were assembled in the same manner as in Example 13 to fabricate a liquid crystal display device of Comparative Example.

(Evaluation of Sensitivity) The curable resin composition 1 obtained in Example 1 was placed on a glass substrate of 10 cm by a spin coater (manufactured by MIKASA, model 1H-DX2).
After coating and drying, a coating film having a dry film thickness of 2 μm was formed. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, the same coating film was divided into four equal parts by a UV aligner (manufactured by Dainippon Screen, model MA 1200) with a photomask placed at a distance of 100 μm from the coating film and equipped with an ultrahigh pressure mercury lamp of 2.0 kW. 2 for each area
Strength of 5, 35, 50, 100 mJ / cm ² (405n
Ultraviolet rays were irradiated at m illuminance conversion).

After irradiation with ultraviolet rays, the coating film was scraped off from each of these four regions into a rectangular shape with dimensions of about 1 mm × 3 mm to partially expose the glass substrate, and a stylus type surface roughness measuring device (Japan Anelva Dektak 160 manufactured by Co., Ltd.
0) was used to measure the film thickness of each irradiation region, which was taken as the film thickness before development.

Then, a 0.05 wt% potassium hydroxide aqueous solution was applied to the exposed portion of the coating film by a spin developing machine (Applied).
Process Technology, INK, M
ODEL: 915) for 60 seconds to dissolve and remove the unexposed area, and the remaining exposed area was washed with pure water for 60 seconds to develop. After development, the exposed film was cleaned in a clean oven (SCOV-250 Hy-manufactured by Ninja Institute).
So), heating at 200 ° C. for 30 minutes. And
The film thickness of each region of the obtained film was measured by the same method as described above, and was taken as the final cured film thickness.

From the film thickness before development and the film thickness after final curing thus measured, the residual film ratio was calculated according to the following equation.

Residual film ratio (%) = (film thickness after final curing (μm)
÷ Film thickness before development (μm) × 100 On the other hand, the reference residual film rate was determined as follows. First, the completely exposed film thickness of the curable resin composition 1 was measured by the same method as the sample except that the entire surface of the coating film was exposed at an intensity of 100 mJ / cm ² . Next, 100 mJ /
cm ^{2 The} exposed coating film was not developed but only heated by the same method as the sample, and the film thickness of the obtained film was measured by the same method as described above to obtain the final film thickness without the development step. . Then, the reference residual film rate was calculated from the measured completely exposed film thickness and the final film thickness without the developing step according to the following equation.

Reference residual film rate (%) = (final film thickness without development step (μm) ÷ complete exposure film thickness (μm)) × 10
0 The smallest exposure amount at which the residual film rate calculated in this way was equal to the reference residual film rate with an error range of 1% was determined as the minimum exposure amount of the curable resin composition 1.

Further, by the same method as described above, the coating films of the curable resin compositions 2 to 4 obtained in the other examples are formed, and the film thickness before development, the film thickness after final curing, and the completely exposed film are formed. Thick,
And the final film thickness without the developing step was measured to determine the minimum exposure amount of each curable resin composition 2 to 4.

Thus, the minimum exposure dose was determined for each curable resin composition 1 to 4. The results are shown in Table 2.

[0255]

[Table 2]

(Evaluation of Elastic Deformation Rate) The fixed spacers of the color filters obtained in Examples 11 and 15 and Comparative Example 3 were polished with a Vickers indenter (quadrangular pyramid shape) to obtain 1
22M in the thickness direction at room temperature using a Fisherscope H-100 manufactured by Fisher Instruments Co., Ltd. equipped with an indenter having a flat surface of 00 μm × 100 μm.
After applying a load up to 2 GPa at a rate of Pa / sec for 5 seconds and then removing the load at a rate of 22 MPa / sec in the thickness direction, the amount of deformation (μm) was measured, and the total amount of deformation shown in FIG. The elastic deformation rate [(T3 / T1) × 100] was calculated by obtaining T1, the plastic deformation amount T2, and the elastic deformation amount T3. The results are shown in Table 3.

[0257]

[Table 3]

(Evaluation of Liquid Crystal Display) The liquid crystal display devices obtained in Examples 13 and 16 and Comparative Example 4 were used to observe the presence or absence of color unevenness due to the difference in the fixed spacers. The results are shown in Table 4.

[0259]

[Table 4]

[0260]

As described above, the curable resin for forming a photosensitive pattern provided by the present invention comprises a structural unit having a cyclic imide group represented by the above formula (1) and an acidic functional group. It is composed of an imide group-containing copolymer having a molecular structure in which the constitutional unit provided and the constitutional unit having a photopolymerizable functional group are linked.

The curable resin composition for forming a photosensitive pattern provided by the present invention contains the curable resin for forming a photosensitive pattern as an essential component, and may contain a photopolymerizable functional group in an amount of 2 if necessary. A polymerizable compound having at least one, and
It is prepared by blending a photopolymerization initiator.

In the curable resin composition for forming a photosensitive pattern of the present invention, a photopolymerizable functional group and a cyclic imide group as a crosslinkable functional group coexist in the molecule of the imide group-containing copolymer as the main polymer. However, due to the high reactivity of the cyclic imide group and the high reaction point density of the cross-linking reaction, the exposure sensitivity is very high even with a small amount of the photopolymerization initiator, and the exposure amount is small, or very high. It can be cured with a short exposure time. Therefore, the time required for pattern formation can be shortened, and the energy for exposure and the amount of photopolymerization initiator used can be saved.

After curing, since the amount of the photopolymerization initiator used is small, yellowing of the cured product, particularly yellowing when used as a protective film or a coloring layer of a color filter, is less likely to occur, and the transparency is improved. Is excellent. Furthermore, the curable resin composition for forming a photosensitive pattern has a cyclic imide group intervening in the cross-linking reaction and a high reaction point density of the cross-linking reaction, so that the coating strength, heat resistance and chemical resistance after curing are high. It has excellent physical properties such as.

Furthermore, when an alcoholic hydroxyl group is contained in the molecule of the imide group-containing copolymer or the polyfunctional polymerizable compound, a radical is generated due to the hydrogen abstraction effect of the imide group, so that a reaction of the crosslinking reaction occurs. Property is further enhanced, and exposure sensitivity and curability are improved.

The curable resin composition for forming a photosensitive pattern of the present invention is particularly suitable for a colored layer of a color filter,
It is suitable as a coating material for forming a protective layer for covering the colored layer and a spacer for maintaining the cell gap of the liquid crystal panel. That is, when the curable resin composition for forming a photosensitive pattern of the present invention is used,
High sensitivity enables high productivity, and excellent coating properties make it possible to form uniform and dimensional-stable colored layers, protective films, and columnar spacers, and the transparency required for colored layers and protective films. Can meet the requirements of

The liquid crystal panel substrate according to the present invention has a plurality of spacers in the non-display area, and the spacers are formed by curing the curable resin composition for photosensitive pattern formation of the present invention. And at room temperature 2.
The elastic deformation rate [(elastic deformation amount / total deformation amount) × 100] with respect to a compressive load of 0 GPa is 60% or more.

The spacer provided on the liquid crystal panel substrate according to the present invention has sufficient hardness to prevent plastic deformation under a compressive load at room temperature, and has liquid crystal shrinkage and expansion 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 pressure unevenness is alleviated or absorbed to make the load uniform over the entire substrate and 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 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 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,
Even if the display area of the liquid crystal display device is large or the cell gap is very narrow, the cell gap can be maintained accurately and uniformly.

Further, the 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 can form an accurate and uniform cell gap without causing plastic deformation when laminating by a room temperature cell pressure bonding method. 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 drive side substrate such as a TFT array substrate is constituted by the 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 uniformly during cell pressure bonding and subsequent handling, so that it is less likely to cause display unevenness and is excellent in image quality.

[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 convex 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) ... Colored layer 8 ... Protective film 9 ... Transparent electrode film 10 ... Alignment film 11 ... Particle spacer 12 ... Column spacer

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) G03F 7/004 505 G03F 7/004 505 (72) Inventor Eiichi Okazaki 1 East of Funami-cho, Minato-ku, Aichi Prefecture Polymer Materials Research Laboratory (72) Inventor Hiromitsu Taguchi 1-1 Funami-cho, Minato-ku, Nagoya City, Aichi Prefecture Toagosei Co., Ltd. Polymer Materials Research Laboratory (72) Inventor Mitsutaka Hasegawa Nagoya, Aichi Prefecture 1 in Funami-cho, Minato-ku, Tochi Gosei Co., Ltd., Polymer Materials Research Laboratory (72) Inventor Shinji Hayashi 1-1-1, Tanikaga-cho, Shinjuku-ku, Tokyo Dai-Nippon Printing Co., Ltd. (72) Inventor Shunsuke Sega 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo F-term (Reference) within Dai Nippon Printing Co., Ltd. (reference) 2H025 AA01 AA04 AA13 AB13 AC01 AD01 BC14 BC53 BC85 BC86 BD43 FA17 2H048 BA02 BA45 BA48 BB01 BB02 BB37 BB42 2H089 LA09 LA10 LA16 LA20 MA07X NA13 NA14 NA17 NA24 QA03 QA11 QA12 QA14 TA07 2H091 FA02Y FB04 FC10 FC26 FC29 FD04 GA08 GA13 4J027 AA02 CB10 CC05 CD06 CD10

Claims (17)

[Claims] 1. At least a constitutional unit having a cyclic imide group represented by the following formula (1), a constitutional unit having an acidic functional group, and a photopolymerizable functional group excluding the cyclic imide group. A curable resin for forming a photosensitive pattern, comprising an imide group-containing copolymer having a molecular structure in which structural units are linked. [Chemical 1] (In the formula, R ³ and R ⁴ are each independently an alkyl group having 4 or less carbon atoms, or either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or each is It is a group that together forms a carbocycle.) 2. The curable composition for forming a photosensitive pattern according to claim 1, wherein the constituent unit having the photopolymerizable functional group has an ethylenically unsaturated bond as a photopolymerizable functional group. resin. 3. The imide group-containing copolymer contains a structural unit represented by the following formula (4) or a structural unit represented by the following formula (5) as a structural unit having a photopolymerizable functional group. The curable resin for forming a photosensitive pattern according to claim 1 or 2, wherein [Chemical 2] (In the formula, R ⁶ and R ⁷ are a hydrogen atom or a methyl group.) (In the formula, R ⁸ and R ¹¹ are a hydrogen atom or a methyl group,
R ⁹ is an alkylene group having 2 to 4 carbon atoms, and R ¹⁰ is an alkylene group. ) 4. The imide group-containing copolymer comprises a structural unit represented by the following formula (2) as a structural unit having a cyclic imide group, and a structural unit represented by the following formula (3) as a structural unit having an acidic functional group. 4. The curable resin for forming a photosensitive pattern according to claim 1, comprising a structural unit represented by the formula (1). [Chemical 4] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 6 carbon atoms, and R ³ and R ⁴ are the same as the above.) (In the formula, R ⁵ is a hydrogen atom or a methyl group.) 5. The curable resin for forming a photosensitive pattern according to claim 1, wherein the imide group-containing copolymer has an alcoholic hydroxyl group in the molecule. 6. A raw material polymer having a molecular structure in which at least a constitutional unit having a cyclic imide group represented by the following formula (1) and a constitutional unit having an acidic functional group are linked to each other, glycidyl acrylate and And / or glycidyl methacrylate are reacted, The manufacturing method of the curable resin for photosensitive pattern formation characterized by the above-mentioned. [Chemical 6] (In the formula, R ³ and R ⁴ are each independently an alkyl group having 4 or less carbon atoms, either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or each is It is a group that together forms a carbocycle.) 7. A molecular structure in which at least a structural unit having a cyclic imide group represented by the following formula (1), a structural unit having an acidic functional group, and a structural unit having a hydroxyl group are linked to each other. A method for producing a curable resin for forming a photosensitive pattern, which comprises reacting a raw material polymer with an isocyanate compound represented by the following formula (6). [Chemical 7] (In the formula, R ³ and R ⁴ are each independently an alkyl group having 4 or less carbon atoms, either one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, or each is Which together form a carbocycle.) (In the formula, R ¹⁰ is an alkylene group, and R ¹¹ is a hydrogen atom or a methyl group.) 8. A curable resin composition for photosensitive pattern formation, comprising the curable resin for photosensitive pattern formation according to claim 1 as an essential component. 9. The elastic deformation rate [(elastic deformation amount / total deformation amount) with respect to a compressive load of 2.0 GPa at room temperature after curing.
X100] shows 60% or more, The curable resin composition for photosensitive pattern formation of Claim 8 characterized by the above-mentioned. 10. The curable resin composition for forming a photosensitive pattern according to claim 8, further comprising a photopolymerizable compound having two or more photopolymerizable functional groups. 11. The photopolymerizable compound according to claim 8, wherein the photopolymerizable compound has three or more ethylenically unsaturated bonds as a photopolymerizable functional group and an alcoholic hydroxyl group. 1. The curable resin composition for forming a photosensitive pattern of. 12. The curable resin composition for forming a photosensitive pattern according to claim 8, further comprising a photopolymerization initiator. 13. A transparent substrate, a colored layer provided on the transparent substrate, and a protective film for covering the colored layer and / or a spacer provided in a non-display area of the substrate. At least one of the colored layer, the protective film and the spacer may be formed by curing the curable resin composition for forming a photosensitive pattern according to any one of claims 8 to 12. A color filter characterized in that 14. The spacer is 2.
The color filter according to claim 13, wherein an elastic deformation rate [(elastic deformation amount / total deformation amount) x 100] is 60% or more with respect to a compressive load of 0 GPa. 15. A non-display area on a substrate is provided with a plurality of spacers, wherein the spacers are the ones according to claim 8 or 1.
It is formed by curing the curable resin composition for forming a photosensitive pattern according to any one of 2 above, and has 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 substrate for a liquid crystal panel. 16. 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, wherein the display side substrate is the color filter according to claim 13. A liquid crystal panel, characterized in that 17. 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 the two, wherein the liquid crystal drive side substrate is the liquid crystal panel according to claim 15. A liquid crystal panel, which is a substrate.