JP2009230116A - Color filter for liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter for a liquid crystal display element capable of obtaining an image of high quality by preventing the swelling of a boundary part between a black matrix and a colored pattern. <P>SOLUTION: In the color filter for the liquid crystal display element having the black matrix and the colored pattern on a translucent substrate, the black matrix has optical density of 3.5 to 8.0 and the difference of heights between a flattened surface of a center part of the colored pattern and the maximum swelling part of an outer peripheral part of the colored pattern is made to be ≤0.5 μm by specifying the film thickness of the black matrix to be 0.8 to 2.0 μm, specifying a horizontal distance from a shoulder part to a lower end of a slope of an end in the width direction of the frame of the black matrix to be 2.5 to 8 μm, specifying a horizontal distance from an outer peripheral line of the colored pattern superposed on the frame to the lower end of the slope to be 3 to 8 μm and specifying the film thickness of the colored pattern to be 1.5 to 2.5 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a color filter for a liquid crystal display element.

  In recent years, in order to improve the contrast of a display image, a black matrix has been required to have a high optical density of 4.0 or more. On the other hand, since the surface smoothness of the color filter is impaired when the thickness of the black matrix is thick, it is necessary to reduce the thickness of the black matrix.

  A metal thin film has been used for producing a black matrix for a display device having high light shielding properties. This is after applying a photoresist on a metal thin film such as chromium formed by vapor deposition or sputtering, and then exposing and developing the photoresist using a photomask having a pattern for a light shielding film for a display device. This is due to a method in which the exposed metal thin film is etched and finally the photoresist remaining on the metal thin film is peeled and removed (see, for example, Non-Patent Document 1).

  Since this method uses a metal thin film, a high light-shielding effect can be obtained even if the film thickness is small, but there is a problem that a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required and the cost is increased. In addition, since it is a metal film, the reflectance is extremely high, and there is a problem that display contrast is lowered under strong external light. Corresponding to these, a method using a low-reflective chromium film (such as one composed of two layers of metal chromium and chromium oxide) has been proposed, but it cannot be denied that the cost is further increased. Furthermore, since the waste liquid containing metal ions is discharged in the etching process, there is a great disadvantage that the environmental load is large. In particular, chromium that is most frequently used is harmful and has a very large environmental impact.

On the other hand, there is a technique using carbon black as one of techniques for obtaining a black matrix with a small environmental load (see, for example, Patent Document 1). In this method, a photosensitive resin composition containing carbon black is applied to a substrate, and the dried product is exposed and developed to form a black matrix.
In addition, it is disclosed that a pixel is tapered to smooth a surface by suppressing a step or the like at a pixel edge (see, for example, Patent Document 2).

  Furthermore, attempts have been made to solve the problem of the rising of the boundary portion by reducing the taper angle of the black matrix (see, for example, Patent Document 3).

JP-A-62-9301 JP-A-8-327814 JP-A-9-113721

“Color TFT LCD” p. 218-p. 220, issued by Kyoritsu Publishing Co., Ltd. (April 10, 1997)

However, in the technique described in Patent Document 1, since the carbon black has a low optical density per unit coating amount, the film thickness inevitably increases when attempting to ensure high light-shielding properties and optical density. If an optical density of 4.0 equivalent to that of a metal film is to be secured, the film thickness becomes 1.0 to 1.5 μm. For this reason, when red, blue, and green pixels are formed after the formation of the black matrix, the surface of the color filter becomes unsmooth due to a step or the like at the pixel edge portion, and there is a disadvantage that the display quality is lowered.
Further, the pixel described in Patent Document 2 has a poor contrast.

  In the method described in Patent Document 3, there are many steps for obtaining the taper angle on the black matrix, and after applying and drying the photosensitive dark color composition for forming the black matrix on the substrate, a positive resist is further applied. It takes time and effort to adjust the developing speed ratio between the photosensitive dark color composition and the positive resist. In addition, only the adjustment of the taper angle is insufficient in suppressing the rise of the colored pattern. Furthermore, this technique is not compatible with large substrates of 1 m × 1 m or more.

  In view of the above circumstances, the present invention is a color filter for a liquid crystal display element that can suppress the rising of the boundary portion between a black matrix and a colored pattern and obtain a high-quality, high-contrast image by a low-cost and simple method. The purpose is to provide.

Specific means for achieving the above object are as follows.
<1> On a light-transmitting substrate, a black matrix formed using a photosensitive dark color composition, and a coloring pattern formed using a photosensitive coloring composition between slanting sections defined by the black matrix; Have
The optical density of the black matrix is 3.5 to 8.0, and the film thickness is 0.8 μm to 2.0 μm; the horizontal distance from the shoulder to the lower end of the inclined surface at the widthwise end of the black matrix frame Is 2.5 μm to 8 μm;
The inclination angle θ ₁ of the inclined surface at the end in the width direction of the black matrix frame is 10 ° ≦ θ ₁ <85 °;
A horizontal distance between the outer peripheral line of the colored pattern overlapping the frame and the lower end of the inclined surface is 3 μm to 8 μm;
A film thickness of the colored pattern is 1.5 μm to 2.5 μm;
The angle θ ₂ between the tangent of the colored pattern and the surface of the light transmissive substrate at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix is 5 ° ≦ θ ₂ <90 °;
Of the pigments contained in the photosensitive coloring composition, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% in the total amount of the pigment, and the primary particle size is 0.08 μm. The proportion of pigment exceeding is less than 5% of the total amount of the pigment;
A color filter for a liquid crystal display element, wherein a difference in height between a flat surface at a central portion of the colored pattern and a maximum raised portion of an outer peripheral portion of the colored pattern is 0.5 μm or less.

  <2> The color filter for a liquid crystal display element according to <1>, wherein the pigment is a pigment coated with a resin.

  <3> The pigment is a compound represented by the following general formula (A), C.I. I. Pigment green 36, or C.I. I. The color filter for a liquid crystal display element according to <1> or <2>, wherein the color filter is Pigment Green 7.

In the general formula (A), R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, —N (CH ₃ ) ₂ , —N (C ₂ H ₅ ) ₂ , —CF ₃ , a chlorine atom, or bromine. Represents an atom.

  <4> The <1> to the above <1>, wherein a photo spacer having an elastic coefficient of 0.8 MPa to 3.0 MPa is provided on the black matrix or a colored pattern formed on the black matrix. 3> The color filter for a liquid crystal display element according to any one of 3>.

<5> The inclination angle θ1 of the inclined surface at the end in the width direction of the frame of the black matrix is 10 ° ≦ θ ₁ ≦ 60 °, and
The angle θ ₂ between the tangent of the colored pattern and the surface of the light-transmitting substrate at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix is 5 ° ≦ θ ₂ ≦ 80 °. The color filter for a liquid crystal display element according to any one of <1> to <4>.

  <6> The color filter for a liquid crystal display element according to any one of <1> to <5>, further including a transparent electrode.

  <7> The color filter for a liquid crystal display element according to any one of <1> to <6>, wherein a width of the black matrix frame is 15 μm to 30 μm.

  According to the present invention, there is provided a color filter for a liquid crystal display element capable of suppressing the rising of a boundary portion between a black matrix and a colored pattern and obtaining a high-quality and high-contrast image by a low-cost and simple method. be able to.

It is a fragmentary sectional view of the color filter which has a horn in an overlap part. It is a fragmentary sectional view of the color filter in which the black matrix was formed. It is a fragmentary sectional view of the color filter in which the overlap part was formed. It is a fragmentary sectional view of the color filter in which the overlap part was formed. It is a fragmentary sectional view of the color filter in which the overlap part was formed. It is a fragmentary sectional view of a black matrix substrate provided with an undercut. It is a fragmentary sectional view of a black matrix substrate provided with an undercut. It is a conceptual diagram of the measuring method for calculating | requiring the height of a horn.

<Color filters for liquid crystal display elements>
(I) The optical density of the black matrix is 3.5 to 8.0 and the film thickness is 0.8 μm to 2.0 μm; (II) The shoulder of the inclined surface at the end in the width direction of the frame of the black matrix (III) The inclination angle θ ₁ of the inclined surface at the end in the width direction of the black matrix frame is 10 ° ≦ θ ₁ <85 °; (IV) The horizontal distance from the outer peripheral line of the colored pattern that overlaps the frame to the lower end of the inclined surface is 3 μm to 8 μm; (V) the film thickness of the colored pattern is 1.5 μm to 2.5 μm; (VI) the colored pattern The angle θ ₂ between the tangent of the colored pattern and the surface of the light-transmitting substrate at the point where the outer peripheral line of the black matrix overlaps the surface of the black matrix is 5 ° ≦ θ ₂ <90 °; (VII) the photosensitive coloring Of the pigments contained in the composition, the primary particle size is 0.02 μm. Less than 10% in the total amount of the pigment, and less than 5% in the total amount of the pigment with a primary particle size greater than 0.08 μm; (VIII) The difference in height between the flat surface at the center of the colored pattern and the maximum raised portion of the outer periphery of the colored pattern is 0.5 μm or less.
The color filter for a liquid crystal display element of the present invention can obtain a color filter for a liquid crystal display element having the characteristics shown in the structural requirement (VIII) by satisfying the structural requirements (I) to (VII). First, the configuration requirement (VIII) will be described.

[(VIII) Difference in height between the flat surface at the center of the colored pattern and the maximum raised portion at the outer periphery of the colored pattern-Tsuno-]
The color filter for a liquid crystal display element according to the present invention uses a black matrix formed using a photosensitive dark color composition on a light-transmitting substrate, and a photosensitive coloring composition between the diagonals defined by the black matrix. The difference in height between the flat surface at the center of the colored pattern and the maximum raised portion of the outer peripheral portion of the colored pattern is 0.5 μm or less.
An outline of the manufacturing process of the color filter will be described with reference to FIG.
In FIG. 1, a photosensitive coloring composition layer is formed by applying a photosensitive coloring composition on a light-transmitting substrate 2 on which a black matrix 4 is formed, and a colored pattern 6 is formed by exposure and development. FIG. 4 is a partial cross-sectional view of a color filter showing a state in which a bulge is generated in a portion where a black matrix 4 and a colored pattern 6 overlap.
When a colored pixel is formed by applying a photosensitive coloring composition on the light-transmitting substrate 2 on which the black matrix 4 is formed, no gap is generated between the frame forming the black matrix 4 and the colored pixel. As described above, the photosensitive coloring composition and the black matrix 4 are overlapped with each other so that the photosensitive coloring composition is slightly covered with the black matrix 4, that is, overlapped. Becomes a state of excitement. Then, the coloring pattern 6 is formed by exposing and developing the layer of the photosensitive coloring composition. By reducing the size of the bulge, it is possible to suppress liquid crystal alignment disorder and light leakage, and undergo an overcoat layer forming step for providing an overcoat layer and a polishing step for polishing the colored pattern surface. High quality images can be obtained without any problems.

The film of the black matrix 4 and the film of the colored pattern 6 are usually formed so that the central part of each film is flat.
The “rise size” refers to the difference in height between the flat surface at the center of the colored pattern 6 and the maximum raised portion at the outer peripheral portion of the colored pattern 6. More specifically, from the distance c in the normal direction of the light-transmitting substrate between the surface of the light-transmitting substrate 2 and the portion of the colored pattern 6 farthest from the surface of the light-transmitting substrate 2, The distance obtained by subtracting the distance d in the normal direction of the light-transmitting substrate between the surface of the substrate 2 and the flat surface of the colored pattern 6 is represented by e in FIG.

Hereinafter, in the present specification, the “swell” is referred to as “horn” for convenience, and the “distance e” is referred to as “horn height”. The height of the horn needs to be 0.5 μm or less in order to obtain a high-quality image. Preferably, it is 0.4 μm or less, and more preferably 0.25 μm or less.
Constitutional requirements of the color filter for liquid crystal display elements of the present invention (I ) To (VII) will be described below.

[(I) Black matrix optical density and film thickness]
The black matrix in the color filter for a liquid crystal display element of the present invention is formed on a light-transmitting substrate using a photosensitive dark color composition, and the optical density of the black matrix is 3.5-8. 0, and the film thickness is 0.8 μm to 2.0 μm.
When the optical density (OD value) is less than 3.5, the display quality of the display device is lowered, such as a reduction in contrast. Further, a black matrix having an optical density exceeding 8.0 can be produced by increasing the film thickness of the black matrix, but it is necessary to use a high-concentration carbon black dispersion liquid due to film thickness restrictions. At this time, if the photosensitive dark color composition is made thick using a high concentration carbon black dispersion so that the optical density exceeds 8.0, light does not reach the light transmissive substrate at the time of exposure. An uncured part is generated and development resistance is deteriorated. That is, the lower part of the photosensitive dark color composition layer is easily slipped off, and an undercut described later becomes large, and as a result, the black matrix is easily chipped.
The optical density (OD value) of the black matrix is preferably 4.0 to 6.0.
The optical density referred to here is the ISO Visual transmission optical density. An example of a measuring instrument that can be used for measuring ISO Visual transmission optical density is X-Rite 361T (V) manufactured by Sakata Inx Engineering Co., Ltd.

Next, the film thickness of the black matrix will be described with reference to FIG.
FIG. 2 is a partial cross-sectional view of the black matrix frame 4 formed on the light-transmitting substrate 2 taken along the width direction of the frame 4. Hereinafter, the “black matrix frame” is also simply referred to as “black matrix”.
In FIG. 2, the film thickness of the black matrix 4 refers to the height of the top surface of the black matrix 4, that is, the vertical distance g from the bottom surface to the top surface of the black matrix 4. In the present invention, the thickness of the black matrix is determined by using a 10-pixel SEM cross-sectional view randomly selected from a color filter in which the black matrix is formed on a light-transmitting substrate. The average value of the film thickness.
The film thickness of the black matrix needs to be 0.8 μm to 2.0 μm, preferably 0.8 μm to 1.5 μm, from the viewpoint of reducing the horn. More preferably, it is 0.8 micrometer-1.2 micrometers.
Within the range of the thickness of the black matrix, the unevenness of the substrate provided with the black matrix, that is, the level difference between the black matrix formation region and the non-formation region is appropriately maintained. The pixel can be formed with high accuracy even when it is formed thereon.

[(II) Horizontal distance from the shoulder to the bottom of the inclined surface at the edge of the width direction of the black matrix frame-slope part, slope length-]
In the color filter for a liquid crystal display element of the present invention, the horizontal distance from the shoulder to the lower end of the inclined surface at the end in the width direction of the frame of the black matrix is 2.5 μm to 8 μm.
This configuration requirement (II) will be described with reference to FIG.

As shown in FIG. 2, the cross section in the width direction of the black matrix 4 includes a bottom surface in contact with the surface of the light transmissive substrate 2, a top surface that is a flat surface at the center of the black matrix 4, and a width direction of the black matrix. It represents from two inclined surfaces located in the edge part. The “horizontal distance from the shoulder to the lower end of the inclined surface at the end in the width direction of the black matrix frame” in the configuration requirement (II) means the shoulder U to the lower end S of one of the two inclined surfaces. Is the horizontal distance f. In other words, the horizontal distance f is the intersection V and the lower end S of the one inclined surface, where V is the intersection of the perpendicular drawn from the shoulder U of the inclined surface to the light transmissive substrate 2 and the surface of the light transmissive substrate 2. And the distance.
The “shoulder of the inclined surface” is an area located at a vertical distance of “the value obtained by multiplying the vertical distance g to the top surface by 0.98” from the bottom surface of the black matrix 4 among the inclined surfaces of the black matrix. Say.
In this specification, “the range 9 of the horizontal distance f” is referred to as “slope portion” for convenience, and “horizontal distance f” is referred to as “slope length” for convenience.

In the present invention, the “horizontal distance from the shoulder to the lower end of the inclined surface at the end in the width direction of the frame of the black matrix”, that is, the slope length needs to be 2.5 μm to 8 μm.
If the slope length is less than 2.5 μm, the horn becomes large, the liquid crystal alignment is disturbed, and the image quality is deteriorated. On the other hand, if the slope length exceeds 8 μm, the contrast decreases due to light leakage from the end portion where the thickness of the black matrix is small, and the end portion of the black matrix is lost during development. The slope length is preferably 3.0 μm to 5.0 μm.
When the slope length is actually obtained, the color filter is cut in a direction perpendicular to the longitudinal direction of the black matrix 4, that is, in the width direction of the black matrix 4, and the cross section is observed and photographed with an SEM and measured. Can be sought.

[(III) Inclination angle θ ₁ of the inclined surface at the end in the width direction of the frame of the black matrix]
In the black matrix in the color filter for liquid crystal display elements of the present invention, the inclination angle θ ₁ of the inclined surface at the end in the width direction of the frame of the black matrix is 10 ° ≦ θ ₁ <85 °.
The inclination angle θ ₁ refers to an angle between a tangent line at the lower end S of the inclined surface of the black matrix 4 and the surface of the light transmissive substrate 2 as shown in FIG.
When the tilt angle θ ₁ is 10 ° ≦ θ ₁ <85 °, the horn can be reduced. The θ ₁ is preferably 10 ° ≦ θ ₁ ≦ 60 °, more preferably 15 ° ≦ θ ₁ ≦ 60 °, and still more preferably 20 ° ≦ θ ₁ ≦ 50 °.
When the “inclination angle θ ₁ ” is actually obtained, it can be obtained by measuring the angle by cutting the color filter in the width direction of the black matrix and taking a photograph of the cross section with an SEM.

Further, the width of the black matrix, that is, the width of the black matrix frame is preferably 15 to 30 μm, from the viewpoint of ensuring brightness by increasing the aperture ratio of the black matrix frame. The width of the black matrix is more preferably 12 μm to 27 μm.
The width of the black matrix means a distance in a direction perpendicular to the longitudinal direction of the black matrix among the distances connecting the lower end of one inclined surface of the black matrix and the lower end of the other inclined surface. For example, the distance between the lower end S of one inclined surface of the black matrix 4 and the lower end S of the other inclined surface in FIG.

[(IV) Range from the outer peripheral line of the colored pattern overlapping the frame and the lower end of the inclined surface -overlapping part-]
In the color filter for a liquid crystal display element of the present invention, a horizontal distance from the outer peripheral line of the colored pattern overlapping the black matrix frame to the lower end of the inclined surface is 3 μm to 8 μm.
As described above, when a photosensitive coloring composition is formed on a light-transmitting substrate on which a black matrix is formed by applying the photosensitive coloring composition, the photosensitive coloring composition is overlapped with the black matrix. Is. By appropriately exposing and developing the photosensitive coloring composition, a colored pattern overlapping with the black matrix can be obtained.
This component (IV) defines the distance that the colored pattern overlaps the black matrix. This configuration requirement (IV) will be described with reference to FIG. FIG. 3 shows a portion of a color filter in which the outer peripheral portion of the colored pattern 6 overlaps the black matrix 4 on the light-transmitting substrate 2 on which the black matrix 4 (black matrix frame 4) is formed. It is sectional drawing.

The coloring pattern 6 covers the black matrix 4 from the lower end S of the inclined surface at the end in the width direction of the black matrix 4 to the outer peripheral line of the coloring pattern 6. The “horizontal distance between the outer peripheral line of the colored pattern overlapping the black matrix frame and the lower end of the inclined surface” in the present configuration requirement (III) is from the lower end S of the inclined surface at the end in the width direction of the black matrix 4. The horizontal distance b to one point T of the outer peripheral line of the coloring pattern 6 is said. The distance b is the shortest distance between the lower end S at the end of the black matrix 4 in the width direction and the point T on the outer peripheral line of the colored pattern 6. Further, the distance b is an inclined surface at the end of the black matrix 4 in the width direction when the intersection point between the perpendicular line drawn from the point T to the light transmissive substrate 2 and the surface of the light transmissive substrate 2 is W. It is the shortest distance from the lower end S.
In this specification, the range 8 of the distance b is referred to as an “overlap portion” for convenience, and the distance b is referred to as “overlap length” for convenience.

The color filter for a liquid crystal display element of the present invention needs to have an overlap length of 3 μm to 8 μm from the viewpoint of reducing the height of the horn. When the overlap length is 3 μm or more, the horn is lowered and the image quality is improved. In addition, when the thickness is 8 μm or less, the color filter and the display device can be stably manufactured on a large substrate (one side of 1 m or more).
The overlap length is preferably 3.0 to 7.0 μm.
When the overlap length is actually obtained, the color filter can be obtained by cutting the color filter in the width direction of the black matrix 4 and observing and photographing the cross section with an SEM.

[(V) Film thickness of colored pattern]
The colored pattern in the color filter for a liquid crystal display element of the present invention is formed using a photosensitive coloring composition on a light-transmitting substrate on which a black matrix is formed, and has a film thickness of 1.5 μm to 2.5 μm. is there.
The film thickness of the coloring pattern refers to the height d of the flat surface at the center of the coloring pattern 6 shown in FIG. In the present invention, the thickness of the colored pattern is determined by using a 10-pixel SEM cross-sectional view randomly selected from the color filter in which the colored pattern is formed on the light-transmitting substrate. The average value of the film thickness.
A pigment dispersion becomes favorable because the film thickness of a coloring pattern is 1.5 micrometers or more. Moreover, it is possible to prevent the cured film (colored pattern and black matrix) on the substrate from being swollen by a solvent such as NMP (n-methylpyrrolidone) after the production of the color filter by being 2.5 μm or less. it can. If the thickness of the colored pattern exceeds 2.5 μm, when the cured film is exposed to a solvent such as NMP, the amount of swelling per unit film thickness of the cured film is apparently increased and the cured film is greatly deformed. The problem which damages the transparent substrate and alignment film which are formed in a post process arises.
The film thickness of the colored pattern is preferably 1.8 μm to 2.4 μm from the viewpoint of reliability such as developability, dispersion stability, and swelling resistance.

[(VI) Angle θ ₂ between the tangent of the colored pattern and the surface of the light-transmitting substrate at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix]
In the color filter for a liquid crystal display element of the present invention, the angle θ ₂ between the tangent of the colored pattern and the surface of the light transmissive substrate at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix is 5 ° ≦ θ ₂ <90 °.
The angle θ ₂ will be described with reference to FIGS. 4 and 5.
4 and 5 are partial cross-sectional views of the color filter showing a state in which the colored pattern 6 is formed so as to overlap the black matrix 4 on the light-transmitting substrate 2 on which the black matrix 4 is formed. . FIG. 4 shows a state in which the outer peripheral line of the colored pattern 6 reaches the top surface of the black matrix 4, and FIG. Indicates the state.

When the outer circumferential line of the colored pattern 6 overlaps the top surface of the black matrix 4, the angle θ ₂ is the colored pattern at the point T where the outer circumferential line of the colored pattern 6 overlaps the top surface of the black matrix 4 in FIG. 6 is an angle between the tangent line 6 and the surface of the light-transmitting substrate 2. When the outer peripheral line of the colored pattern 6 overlaps the inclined surface at the end in the width direction of the black matrix 4, the outer peripheral line of the colored pattern 6 is the inclined surface at the end in the width direction of the black matrix 4 in FIG. The angle between the tangent line of the colored pattern 6 at the point X overlapping with the surface of the light transmissive substrate 2.
When the θ ₂ is 5 ° ≦ θ ₂ <90 °, the transparent substrate is sufficiently deposited. The θ ₂ is preferably 5 ° ≦ θ ₂ ≦ 80 °, and more preferably 5 ° ≦ θ ₂ ≦ 60 °.
When the “angle θ ₂ between the tangent of the colored pattern and the surface of the light-transmitting substrate at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix” is actually obtained, It can be determined by measuring the angle by cutting in the width direction and taking a cross-section of the cross-section with a SEM.
Next, the photosensitive coloring composition used for manufacture of the color filter for liquid crystal display elements of this invention and the photosensitive dark color composition are demonstrated in detail.

<Photosensitive coloring composition>
The photosensitive coloring composition used for forming the coloring pattern of the color filter of the present invention is a radiation-sensitive composition (for example, in the case of a negative type, a radiation-sensitive composition that is cured by light), and (A -1) It preferably contains a colorant, (B) an alkali-soluble resin, (C-1) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Other additives such as a molecular dispersant and a surfactant may be contained.

-(A-1) Colorant-
As the colorant, a dye / pigment system can be appropriately selected, and the pigment used as the colorant may be an inorganic pigment or an organic pigment. Use of a small particle size is preferred. The average particle size is preferably 10 nm to 100 nm, more preferably 10 nm to 50 nm.
Furthermore, in the color filter for liquid crystal display elements of the present invention, the proportion of the pigment having a primary particle size of less than 0.02 μm among the pigments contained in the photosensitive coloring composition is less than 10% in the total amount of the pigment. And the proportion of the pigment having a primary particle diameter exceeding 0.08 μm is required to be less than 5% in the total amount of the pigment (constituent requirements for the color filter for liquid crystal display element of the present invention (V )).
In the photosensitive coloring composition used in the present invention, by using a polymer dispersing agent described later, even when the size of the coloring agent is small, the pigment dispersibility and dispersion stability are improved. Even if the thickness is small, a colored pixel having excellent color purity can be formed.

[(VII) Pigment ratio]
As described above, in the color filter for a liquid crystal display element of the present invention, among the pigments contained in the photosensitive coloring composition, the proportion of the pigment having a primary particle diameter of less than 0.02 μm is in the total amount of the pigment. The proportion of the pigment that is less than 10% and the primary particle diameter exceeds 0.08 μm needs to be less than 5% in the total amount of the pigment.
When the ratio of the pigment having a primary particle diameter of less than 0.02 μm is less than 10%, the heat resistance and chromaticity change can be prevented, and the ratio of the pigment having a primary particle diameter exceeding 0.08 μm is 5 When it is less than%, the contrast is good, the time-dependent stability of the photosensitive coloring composition coating solution is good, and foreign matter failure can be prevented.
The proportion of the pigment having a primary particle size of less than 0.02 μm is preferably less than 5% from the viewpoints of heat resistance and chromaticity change prevention.
The proportion of the pigment having a primary particle diameter exceeding 0.08 μm is preferably less than 3% from the viewpoint of improving the contrast.

  The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, the TEM photograph is subjected to image analysis to examine the particle size distribution. For example, the particle size distribution can be grasped by measuring the total number of particles in the observation sample at 30,000 times to 100,000 times and the number of pigment particles less than 0.02 μm and more than 0.08 μm.

A transmission electron microscope is suitable for observing the primary particle diameter of the pigment. For example, the total number of particles in the observation sample at 30,000 times to 100,000 times, and particles of the pigment exceeding 0.02 μm and exceeding 0.08 μm The particle size distribution can be grasped by measuring the number.
Regarding the primary particle size, the ratio of primary particles less than 0.02 μm and the ratio of primary particles exceeding 0.08 μm are obtained by observing the pigment powder with a transmission electron microscope, measuring the major axis of each primary particle, It can be obtained by calculating the proportion (number%) of pigment particles less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder is observed with a transmission electron microscope at 30,000 to 100,000 times, photographed, the major axis of 1000 primary particles is measured, less than 0.02 μm, and 0.08 μm The ratio of primary particles exceeding is calculated. This operation was performed for a total of three locations with different pigment powder locations, and the results were averaged.

  Examples of the inorganic pigment that can be used as a colorant for forming a colored pattern (colored pixel) include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium And metal oxides such as lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Moreover, as an organic pigment, for example,
CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110,
138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
CI Pigment Orange 36, 38, 43, 71;
CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
CI pigment violet 19, 23, 32, 37, 39;
CI Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CI Pigment Green 7, 36, 37;
CI Pigment Brown 25, 28;
CI Pigment Black 1
And compounds represented by the following general formula (A).

In the general formula (A), R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, —N (CH ₃ ) ₂ , —N (C ₂ H ₅ ) ₂ , —CF ₃ , a chlorine atom, or bromine. Represents an atom.
Among these, R is preferably a chlorine atom, a hydrogen atom, a methyl group, or a phenyl group.

Although it does not specifically limit in this invention, The following pigment is more preferable.
A compound represented by the general formula (A);
CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;
CI Pigment Orange 36, 71;
CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242;
CI pigment violet 19, 23, 37;
CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CI Pigment Green 7, 36, 37;

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a pigment for the red phase (R), a compound represented by the general formula (A), an anthraquinone pigment, a perylene pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, A mixture with a quinophthalone yellow pigment or a perylene red pigment can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment red 224, and examples of the compound represented by the general formula (A) include C.I. I. Pigment Red 254 (R in the general formula (A) is a chlorine atom), and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  In addition, as a pigment for the green phase (G), a halogenated phthalocyanine pigment alone or a mixture thereof with a bisazo yellow pigment, quinophthalone yellow pigment, azomethine yellow pigment or isoindoline yellow pigment may be used. Can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the pigment for the blue phase (B), a phthalocyanine pigment can be used alone or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  The content of (A-1) the colorant (pigment) in the photosensitive coloring composition layer used in the present invention is 25% by mass to 75% by mass with respect to the total solid content (mass) of the composition. Is preferable, and 32 mass%-70 mass% is more preferable. (A-1) When the content of the colorant (pigment) is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

  In the present invention, it is particularly preferable to use an organic pigment as a colorant and to coat the pigment with a polymer compound in the pigment miniaturization step or dispersion step. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles Further, it is possible to use a coated pigment excellent in dispersion stability in which primary particles are stably maintained.

  The coated pigment, which is a preferred embodiment in the present invention, is a pigment coated with a polymer compound. However, the coating is a new interface of a highly active pigment generated by miniaturization and the side chain of the present invention. It is considered that a coating pigment having higher dispersion stability can be obtained because a strong coating layer of the polymer compound is formed by a strong electrostatic action with the polymer compound having a heterocyclic ring. That is, in the present invention, the coated polymer compound is hardly liberated even when the pigment after coating treatment is washed with an organic solvent that dissolves the polymer compound.

  The coated pigment as used in the present invention is one in which pigment particles such as organic pigments are coated with a polymer compound having a polar group such as a heterocyclic ring in the side chain, and the polymer compound is a part of the pigment particle surface or By being firmly coated all over, a higher dispersion stability effect can be obtained, which is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent described below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a surface-coated pigment as in the present invention, the liberation rate Is very small, 30% or less.

  The pigment after the coating treatment is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours using a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. And calculated as “mass of the polymer compound used in the initial treatment”. Separately, the pigment is washed with 1-methoxy-2-propanol, and the obtained liberation amount is divided by the “mass of the polymer compound used in the initial treatment” to obtain the liberation rate (%). .
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. The preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The coating treatment is preferably performed at the same time in the step of refining the pigment. Specifically, i) the pigment, ii) the water-soluble inorganic salt, and iii) a small amount of water-soluble that does not substantially dissolve ii). An organic solvent, and iv) a step of adding a polymer compound and mechanically kneading with a kneader or the like (referred to as a salt milling step), adding this mixture into water, stirring the mixture with a high-speed mixer or the like to form a slurry, The slurry is filtered, washed with water, and dried if necessary.

The salt milling described above will be described more specifically. First, add a small amount of iii) a water-soluble organic solvent as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, knead strongly with a kneader, etc., and then throw this mixture into water. Stir with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When used in an oily varnish, it is possible to disperse the treated pigment before drying (referred to as filter cake) in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.
During salt milling, iii) by using an organic solvent in combination with iv) at least partly soluble resin, the pigment is agglomerated during drying, and the surface is further coated with iv) at least partly soluble resin. Can be obtained.
Note that iv) the polymer compound may be added at the initial stage of the salt milling process, or may be added separately. It is also possible to add in the dispersion step.

  The polymer compound used for coating the pigment may be anything as long as it has an adsorptive group for the pigment. In particular, those coated with a polymer compound having a heterocyclic ring in the side chain are preferred. Such a polymer compound is preferably a monomer represented by the following general formula (1) or a polymer containing a polymer unit derived from a monomer comprising a maleimide or a maleimide derivative. A polymer containing a polymer unit derived from the monomer represented by the general formula (1) is particularly preferable.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
As the alkyl group for R ¹ , an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of preferable alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ¹ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
The alkylene group represented by R ² may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the above alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

  In general formula (1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, indanthrone series, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

  Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formulas (2), (3), and (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  Specific examples of these compounds include the following MA-1 to MA-13 and the following M-1 to M-33, but the present invention is not limited thereto.

  In addition to the MA-1 to MA-13 and M-1 to M-33, the following compounds can be exemplified.

Even in the case of using the above-described coated pigment, it is more preferable to disperse the pigment using at least one dispersant and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.), etc. Anionic surfactants; EFKA-4 , EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15 , Disperse Aid 9100 (all manufactured by San Nopco Co., Ltd.) and the like; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, and other various Solsperse dispersants (Nippon Lubrizol ( Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P 123 (manufactured by Asahi Denka Co., Ltd.) and Ionnet S-20 (manufactured by Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

  A pigment derivative is added to the above-described pigment dispersion composition as necessary. The pigment is introduced into the curable composition as fine particles by adsorbing a pigment derivative having a part having affinity for the dispersant or a polar group to the pigment surface and using it as an adsorption point of the dispersant. The re-aggregation can be prevented, and it is effective for constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The dispersion method can be performed, for example, by finely dispersing a pigment and a dispersant previously mixed with a homogenizer or the like using a bead disperser using zirconia beads or the like.

-(B) Alkali-soluble resin-
The photosensitive coloring composition of the present invention preferably contains an alkali-soluble resin (binder polymer) for the purpose of improving film properties and imparting development properties.
The alkali-soluble resin used in the present invention is a linear organic polymer, and at least one molecule in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

More preferable as the alkali-soluble resin are polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, croton as described in JP-A Nos. 59-53836 and 59-71048. Acrylic polymers such as acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added The thing of a copolymer is mentioned.
The acid value is preferably in the range of 10 mgKOH / g to 200 mgKOH / g, preferably 30 mgKOH / g to 180 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Examples of the alkyl (meth) acrylates and aryl (meth) ^{_{acrylate, CH 2 = C (R 1}} ) (COOR 3) [wherein, ^{R 1} represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, ^{R 3} Represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferable. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. These OH group alkyl-blocked compounds such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate and the like are used as copolymerization components. An acrylic copolymer.

As the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. . Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
Other monomers that can be copolymerized can be used singly or in combination of two or more. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.

As described above, the acrylic resin has an acid value in the range of 20 mgKOH / g to 200 mgKOH / g. If the acid value is 200 mgKOH / g or less, the acrylic resin does not become too soluble in alkali, and the appropriate development range (development latitude) can be prevented from becoming narrow. On the other hand, if it is 20 mgKOH / g or more, the solubility in alkali is unlikely to be reduced, so that it is possible to prevent the development time from being prolonged.
In addition, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used to realize a viscosity range in which the photosensitive coloring composition can be easily used in the process such as coating, and the film strength is secured. Therefore, it is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

  In order to improve the crosslinking efficiency of the photosensitive coloring composition in the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin having no polymerizable group. A polymer containing a group, a (meth) acryl group, an aryloxyalkyl group or the like in the side chain is useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as each molecule contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond. .

(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin, (2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule,
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

Examples of compounds having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd.); Biscote R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel)・ Cytech Co., Ltd.).
As addition amount of alkali-soluble resin, it is preferable that it is the range of 3-30 mass% in the total solid of a photosensitive coloring composition layer, and 5-20 mass% is more preferable.

In preparing the photosensitive coloring composition, it is preferable to add the following epoxy resin as a binder polymer in addition to the alkali-soluble resin. Examples of the epoxy resin include compounds having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Toto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. Daicel Chemical Industries, Ltd.) and the like, and bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.

Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel Cytec Co., Ltd.) can also be used. Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Toto Kasei Co., Ltd.), Denacol EM-125, etc. (above, manufactured by Nagase ChemteX) As the biphenyl type, 3,5,3 ′, 5′-tetramethyl-4,4 ′
-Examples of alicyclic epoxy compounds such as diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above, Daicel Chemical Industries ( Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (above, manufactured by Toto Kasei Co., Ltd.), Epiclon 430, 673, 695, 850S, 4032 (above, large) Nippon Ink Chemical Co., Ltd.). Also 1, 1, 2, 2
-Tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and other amine-type epoxy Epototoy YH-434 and YH-434L which are resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin, and the like can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, and the shrinkage during curing is large.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl. -4,4 'diglycidyl biphenyl, celoxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

-(C-1) polymerizable compound-
The photosensitive coloring composition used in the present invention preferably contains (C-1) a polymerizable compound.
The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(However, R ⁴ and R ⁵ each independently represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final photosensitive material. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the colored image portion, that is, the photosensitive coloring composition layer, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic ester, methacrylic ester, A method of adjusting both sensitivity and strength by using a styrene compound or a vinyl ether compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, selection and use of addition polymerization compounds for compatibility and dispersibility with other components in the photosensitive coloring composition layer (for example, alkali-soluble resin, initiator, colorant (pigment, dye, etc.)) Is an important factor, for example, compatibility may be improved by the use of low-purity compounds or a combination of two or more, and a specific structure is selected for the purpose of improving adhesion to the substrate. It can happen.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are preferable, and commercially available products include urethane oligomer UAS-10, UAB-140 (Nippon Paper Chemical Co., Ltd.). Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) are preferable.

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha) Chemical Co., Ltd.) is more preferable.

  (C-1) The content of the polymerizable compound is preferably 5% by mass to 55% by mass and preferably 10% by mass to 50% by mass in the total solid content in the photosensitive coloring composition layer of the present invention. It is more preferable that it is 15 mass%-45 mass%.

-(D) Photopolymerization initiator-
The photosensitive coloring composition of the present invention preferably contains (D) a photopolymerization initiator.
The photopolymerization initiator is a compound that is decomposed by light and starts and accelerates the polymerization of the polymerizable compound (C-1), and preferably has an absorption in a wavelength region of 300 to 500 nm. Moreover, the said photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

Specific examples of organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc.
Japan 42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55-3070, JP JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243 JP, 63-298339, M .; P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. It is done.

Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol) Linophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, p-dimethyl Examples thereof include benzoic acid ester derivatives such as ethyl aminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl dimethyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4- Di (9-acridinyl) butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di ( 9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9- Acridinyl) dodecane and other di (9-acridinyl) alkanes.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, oxalic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 -Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), And carbonyldi (t-hexylperoxydihydrogen diphthalate).

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- -Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaph Orofen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 5'-tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include, for example, JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, and JP-A-9-188710. JP, 2000-131837, JP 2002-107916, JP 2764769, JP 2002-116539, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19 -22, 1998, Chicago ”etc., organic boron sulfonium complexes or organic boron described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561. Oxosulfonium complex, JP-A-6-175554 JP, JP-A-6-175553, organoboron iodonium complex, JP-A-9-188710, organoboron phosphonium complex, JP-A-6-348011, JP-A-7-128785, JP Specific examples include organoboron transition metal coordination complexes such as 7-140589, JP-A-7-306527, and JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797 And the compounds described. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055 and 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, JP-A-2-150848, and JP-A-2-296514. Examples thereof include iodonium salts described in the publication.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. .

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297. 442, U.S. Pat. Nos. 4,933,377, 4,760,013, 4,734,444, 2,833,827, Germany Examples include sulfonium salts described in Patent Nos. 2,904,626, 3,604,580, and 3,604,581 from the viewpoint of stability and sensitivity. It is preferably substituted with an electron-withdrawing group. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferred sulfonium salt, a sulfonium salt having absorption at 300 nm or more having a triarylsulfonium salt having an aryloxy group or an arylthio group as a substituent can be mentioned.

Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello
et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  (D) As a photopolymerization initiator, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound Oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3- Compounds selected from the group consisting of aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalomethyl compounds. Most preferred is at least one compound selected from the group consisting of triazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds.

  (D) It is preferable that content of a photoinitiator is 0.1 mass%-20 mass% with respect to the total solid in a photosensitive coloring composition layer, More preferably, 0.5 mass%-15 It is 1 mass%-10 mass% especially preferably. Within this range, good sensitivity and pattern formability can be obtained.

-(E) Solvent-
The photosensitive coloring composition used in the present invention can generally be prepared using a solvent.
Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. 3-oxypropionic acid alkyl esters (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, -2-oxypropionic acid alkyl esters such as ethyl oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion) Acid methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate, etc.), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl Ether acetate, propylene glycol propyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n -Propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether Acetate, tripropylene glycol mono n-butyl ether, tripropylene glycol methyl ether acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether,
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

-Other additives-
In addition to the above components, various known additives can be used in the photosensitive coloring composition used in the present invention depending on the purpose.
Hereinafter, such additives will be described.

(Dispersant)
The photosensitive coloring composition in the present invention preferably contains a polymer dispersant. This polymer dispersant is a resin having a weight average molecular weight in the range of 3,000 to 100,000. Furthermore, it is preferable that an acid value is 20 mgKOH / g-300 mgKOH / g. Hereinafter, such a specific polymer dispersant may be simply referred to as “dispersion resin”.
The dispersing resin in the present invention is a pigment dispersing agent mentioned as the colorant (A-1) or a photosensitive dark color composition for forming a black matrix, which will be described later. It is a compound that can function as a dispersant.
Since the dispersion resin needs to have a specific acid value, it is preferably a polymer compound having an acidic group.

  Examples of the polymer skeleton of the polymer compound include polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified products thereof. Or a copolymer [for example, a polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, etc. (any of a random copolymer, a block copolymer, and a graft copolymer) Good). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.

Examples of a method for introducing an acidic group into the polymer skeleton as described above include, for example, a method of copolymerizing a monomer containing an acidic group when polymerizing the polymer skeleton, and the polymer described above. There is a method of introducing a skeleton by polymer reaction after polymerization.
Examples of the monomer containing an acidic group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, styrene sulfonic acid, 2-acrylamide-2- It is obtained by reacting an alcoholic hydroxyl group-containing monomer such as methylpropanesulfonic acid, mono (meth) acryloyl ethyl phosphate, or 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. And monomers.

Furthermore, the polymer compound having an acidic group may further contain a vinyl monomer component as a copolymerization component.
The vinyl monomer is not particularly limited. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

  Preferred examples of the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. Sulfuric acid ester groups, phosphoric acid groups, and monophosphoric acid ester groups are more preferable, and carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups are particularly preferable.

In addition, the polymer dispersant in the present invention preferably contains a group having a basic nitrogen atom in order to improve dispersibility. The group having a basic nitrogen atom is, for example, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ or —NR ⁹ R ¹⁰ ; where R ⁸ , R ⁹ , and R ¹⁰ are each Independently, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following chemical formula (a1), or the following chemical formula Preferred examples include the amidinyl group represented by (a2).

In the chemical formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In the chemical formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , or —NR ⁹ R ¹⁰ ; where R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. A guanidyl group represented by the chemical formula (a1) [in the chemical formula (a1), R ¹¹ and R ¹² are each independently an alkyl having 1 to 10 carbon atoms. Represents a group, a phenyl group, or a benzyl group. ] An amidinyl group represented by the chemical formula (a2) [in the chemical formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. And the like include groups consisting of 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms, which may be unsubstituted or may further have a substituent.

(Other dispersants)
The photosensitive coloring composition used in the present invention can be used in combination with a conventionally known dispersant (pigment dispersant) in addition to the dispersion resin.

Known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymers], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of known dispersants (pigment dispersants) that can be used in the present invention include "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166" manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd., Poly Low No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ”manufactured by Enomoto Kasei Co., Ltd.,“ “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “acetamine 86 (stearylamine acetate)”, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)”, 13240 (manufactured by Nippon Lubrizol) Polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemical Co., Ltd. ) , MYS-IEX (polyoxyethylene monostearate) ”and the like.

  The known dispersing agent as described above is 10% by mass to 100% by mass with respect to the dispersing resin as necessary, that is, in the range of dispersing agent / dispersing resin = 1/10 to 1/1 (equivalent). Can be used.

(Surfactant)
When the pigment concentration is increased, the thixotropy of the coating solution is generally increased. Therefore, film thickness unevenness after the photosensitive colored composition layer (colored layer coating film) is formed by applying or transferring the photosensitive colored composition on the substrate. It is easy to produce. In particular, in the formation of the photosensitive coloring composition layer (colored layer coating film) by the slit coating method, the coating liquid for forming the photosensitive coloring composition layer may be leveled before drying to form a coating film having a uniform thickness. is important. For this reason, it is preferable to contain an appropriate surfactant in the photosensitive coloring composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, the Adeka Pluronic series, the Adecanol series, the Tetronic series (above made by ADEKA), the Emulgen series, the Leodore series (above made by Kao Corporation), the Eleminor series, and the Nonipole series. , Octopole series, Dodecapol series, New Pole series (above Sanyo Kasei Co., Ltd.), Pionein series (above Takemoto Yushi Co., Ltd.), Nissan Nonion series (above Nihon Yushi Co., Ltd.), etc. . These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08 (Dainippon Ink Co., Ltd.), Florard FC -135, FC-170C, FC-430, FC-431 (Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801 and 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above , Momentive Performance Materials Japan).

  These surfactants are preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the coating liquid for forming the photosensitive coloring composition layer. When the amount of the surfactant exceeds 5 parts by mass, surface roughness is likely to occur during coating and drying, and the smoothness tends to deteriorate.

  In addition, in order to promote alkali solubility of the uncured part and further improve the developability of the photocurable composition, addition of an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a weight average molecular weight of 1000 or less Can be performed. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

(Alkoxysilane compound)
In the photosensitive coloring composition used in the present invention, an alkoxysilane compound, especially a silane coupling agent, can be used from the viewpoint of improving adhesion to the substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material, and (meth) acryloyl or phenyl exhibiting affinity through interaction or bond formation with an organic resin. , Mercapto and epoxysilane, and (meth) acryloylpropyltrimethoxysilane is more preferable among them.
As the addition amount in the case of using a silane coupling agent, the total solid content in the photosensitive coloring composition layer used in the present invention is preferably in the range of 0.2% by mass to 5.0% by mass, 0.5 mass%-3.0 mass% are more preferable.

(Co-sensitizer)
The photosensitive coloring composition used in the present invention preferably contains a co-sensitizer if desired. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the initiator to actinic radiation or suppressing inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. , JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is from 0.1% by mass to 30% by mass with respect to the mass of the total solid content of the curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range is preferable, the range of 0.1% by mass to 25% by mass is more preferable, and the range of 0.5% by mass to 20% by mass is still more preferable.

(Polymerization inhibitor)
In the present invention, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the photosensitive coloring composition. Is desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, phenoxazine, phenothiazine and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass in the photosensitive coloring composition layer. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

(Plasticizer)
Furthermore, in the present invention, in order to improve the physical properties of the photosensitive coloring composition layer, an inorganic filler, a plasticizer, a fat-sensitizing agent that can improve the ink inking property on the surface of the photosensitive layer, and the like may be added. .
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

  By using the above-described components, the photosensitive coloring composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to a board | substrate is shown. Therefore, the photosensitive coloring composition containing the various components can be preferably used for a color filter.

<Photosensitive dark color composition>
The photosensitive dark color composition used in the present invention comprises (A-2) a light-shielding agent, (B) an alkali-soluble resin, (C-2) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. It is preferable to contain, and other additives, such as a dispersing agent and surfactant, can be contained as needed.

-(A-2) Shading agent-
(A-2) Examples of the light-shielding agent include carbon black, titanium black, metal fine particles, metal oxides, and sulfide fine particles in addition to the colorant (A-1). The optical density (OD value) of the black matrix in the color filter for a liquid crystal display element of the present invention is not particularly limited as long as it can be set to 3.5 to 8.0. ) Is preferably 3.5 to 8.0, and carbon black that is excellent in the balance between light shielding properties and cost is particularly preferable.
These are used singly or in combination as required. For example, carbon black alone, a mixture of organic pigments, and a combination of carbon black and organic pigments.
As a light-shielding material, conventionally, as a black colorant, at least two kinds of pigments have been used in combination so as to shield the visible light region. Examples of these pigments include the pigments described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-17521 [0080] to [0088]. The formation of the used light shielding layer is disclosed in JP-A-7-271020.
In order to further increase the light shielding effect, in Japanese Patent Laid-Open No. 2000-147240, Japanese Patent Laid-Open No. 2000-143985, Japanese Patent Laid-Open No. 2005-338328, Japanese Patent Laid-Open No. 2006-154849, etc., carbon black, titanium black, or graphite is a suitable light-shielding material. Has been developed as. In the present invention, carbon black is preferable as one of the light shielding materials from the viewpoint of light shielding properties and cost.

As an example of carbon black, pigment black 7 (carbon black) is preferable. Examples of the carbon black include carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, #M manufactured by Mitsubishi Chemical Corporation. 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP; Degussa Carbon Black Color
Black FW200, Color Black FW2, Color Black
FW1, Color Black FW18, Color Black S170, Color Black S160, Special Black6, Special Black5, Special Black4, Special BlackU, P 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, BLACK PEARLS 1400; carbon black SUNBLACK900, 910, 930, 960, and 970 manufactured by Asahi Carbon Co. Also preferred are those coated with a polymer compound in order to increase the electric resistance. The preferred single particle size of these carbon blacks is 10 to 100 nm, more preferably 10 to 50 nm.

-(C-2) polymerizable compound-
As the polymerizable compound (C-2) polymerizable compound in the photosensitive dark color composition for forming the black matrix, the polymerizable compound (C-1) used in the photosensitive coloring composition is also preferable. The following are particularly preferable.
The polymerizable compound in the photosensitive dark composition is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

An acidic polyfunctional photocurable compound is also a preferred compound. Examples of the acidic polyfunctional photocurable compound include (1) a monomer or oligomer having a hydroxyl group and three or more photocurable functional groups, which is modified with a dibasic acid anhydride to introduce a carboxyl group, (2) Introducing a carboxyl group by adding a compound having a glycidyl group or an isocyanate group and a COOH group to a monomer or oligomer having a hydroxyl group and three or more photocurable functional groups, or (3) three or more Those having a sulfonic acid group introduced by modifying an aromatic compound having a photocurable functional group with concentrated sulfuric acid or fuming sulfuric acid can be used. Moreover, you may use the oligomer which contains the monomer which is an acidic polyfunctional photocurable compound itself as a repeating unit as an acidic polyfunctional photocurable compound.
As an example of an acidic polyfunctional photocurable compound, what is represented by the following general formula (i) and general formula (ii) is preferable. In general formula (i) and general formula (ii), when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X, and W.

In general formula (i), R represents a (meth) acryloyloxy group, and X represents a —COOH group or an —OPO ₃ H ₂ group. T represents an oxyalkylene group, wherein the alkylene group has 1 to 4 carbon atoms. n is 0-20.
In general formula (ii), W represents R or X in general formula (i), and 3 or more Ws are R among 6 Ws. G is synonymous with T in the general formula (i). Z is, -O- or represents _{-OC = ONH (CH 2) qNHCOO-} . p is 0-20 and q is 1-8. A plurality of R, T, G, and W present in one molecule may be the same or different.

  As a commercial item of the acidic polyfunctional photocurable compound represented by general formula (i) and general formula (ii), for example, TO-756 which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and And TO-1382 which is a carboxyl group-containing pentafunctional acrylate.

  Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, the above carboxyl group-containing pentafunctional acrylate, etc. Is preferred. In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  The content of the polymerizable compound (C-2) in the photosensitive dark composition used for forming the black matrix is 5% by mass to 50% by mass in the total solid content of the photosensitive dark color composition layer. It is preferably 7% by mass to 40% by mass, more preferably 10% by mass to 35% by mass.

The (B) alkali-soluble resin, (D) polymerization initiator, (E) solvent, and other additives used in the photosensitive dark color composition are the same as those in the above-described photosensitive coloring composition for forming a colored pattern. The preferable content is also the same.
Next, the manufacturing method of the color filter for liquid crystal display elements of this invention is demonstrated.

<Method for producing color filter for liquid crystal display element>
The color filter for a liquid crystal display element of the present invention forms a black matrix on a light-transmitting substrate using a photosensitive dark color composition (black matrix forming step), and further a photosensitive coloring composition on the black matrix. It can manufacture by forming a colored pattern using (coloring pattern formation process), However, Another process can also be provided as needed.
Hereinafter, the black matrix forming step and the colored pattern forming step will be described separately.

[Black matrix formation process]
In the black matrix, a photosensitive dark color composition layer is formed on a light-transmitting substrate using a photosensitive dark color composition (photosensitive dark color composition layer forming step), and the photosensitive dark color composition layer is formed. By exposing (exposure process), developing the photosensitive dark color composition layer after the exposure (development process), forming a black matrix pattern, and baking the formed black matrix pattern (baking process) A black matrix can be formed. In addition to the above steps, the black matrix forming step may be provided with other steps as necessary.

-Photosensitive dark color composition layer forming step-
Examples of the light-transmitting substrate (hereinafter also simply referred to as “substrate”) that can be used in this step include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like used in liquid crystal display elements. Examples include a substrate to which a transparent conductive film is attached and a photoelectric conversion element substrate used for a solid-state imaging element. Furthermore, a plastic substrate is also possible. In these substrates, first, a black matrix is formed in a lattice shape so as to isolate each pixel, and colored pixels are formed in the empty portions of the lattice.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with an upper layer, prevent diffusion of substances, or planarize the substrate surface. It is preferable that the substrate is large (generally 1 m or more per side) in that the effects of the present invention are further exhibited.

As a method of forming the photosensitive dark color composition layer on the substrate, for example, there is a method of applying the photosensitive dark color composition on the substrate by coating or the like.
As a method for applying the photosensitive dark color composition on the substrate, various application methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied. Of these, slit coating is preferred from the viewpoints of accuracy and speed.
Moreover, the method of transferring the coating film previously formed on the temporary support by the above application method onto the substrate can also be applied.
Regarding the transfer method, paragraph numbers [0023] and [003] of JP-A-2006-23696.
6] to [0051] and the production methods described in paragraph numbers [0096] to [0108] of JP-A-2006-47592 can be suitably used in the present invention.

  As described above, in the color filter for a liquid crystal display element of the present invention, the film thickness of the black matrix needs to be 0.8 μm to 2.0 μm. In order to make the film thickness of the black matrix within the above range, it is preferable to control the thickness when the photosensitive dark color composition is applied onto the substrate. That is, the thickness (for example, coating thickness) when the photosensitive dark color composition is applied onto the substrate is appropriately adjusted according to the design value of the thickness of the black matrix to be formed, but generally 0.2 μm. -2.2 μm is preferable, and 0.8 μm-1.5 μm is most preferable.

-Exposure process-
In the exposure step, the photosensitive dark color composition layer formed in the photosensitive dark color composition layer forming step is exposed through a predetermined mask pattern, and patterned (in the case of a negative type, light irradiation is performed). Only the coating film portion is cured). As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used. Irradiation dose is preferably from ^{5mJ / cm 2 ~500mJ / cm 2} , more preferably ^{10mJ / cm 2 ~300mJ / cm 2} , 10mJ / cm 2 ~200mJ / cm 2 being most preferred.
The exposure machine can be a proximity type exposure machine, a mirror projection system, or a stepper system.

-Development process-
Next, by performing an alkali development treatment, for example, when the photosensitive dark color composition is a negative type, the non-light-irradiated part in the exposure may be eluted in an alkaline aqueous solution, leaving only the photocured part. it can.
As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is used.
Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001 to 0.001. An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

In the formation of the black matrix in the present invention, the slope portion length of the black matrix is adjusted to 2.5 μm to 8 μm, and the inclination angle θ ₁ of the inclined surface at the end in the width direction of the black matrix frame is set to 10 ° ≦ θ _In order to adjust ₁ <85 °, it is preferable to provide the following steps. That is, it is possible to provide a step of forming a black matrix pattern so that the length of the undercut of the black matrix is 1.0 μm to 8.0 μm after the main development step and before the baking step described later. preferable. By providing such a step, it becomes easy to adjust the height of the horn to 0.5 μm or less.
The shape of the black matrix pattern, particularly the undercut shape, can be controlled by the conditions of exposure, development, and pre-baking described later. First, the undercut will be described in detail.

In the black matrix formation process, when developing the photosensitive dark color composition layer after exposure, the surface of the photosensitive dark color composition layer (refers to the surface not in contact with the substrate; hereinafter the same applies to the black matrix) And the back side of the photosensitive dark color composition layer (in contact with the substrate) as compared with the inside of the layer close to the front surface (hereinafter referred to as “photosensitive dark color composition layer upper part”, and the black matrix is also referred to as “black matrix upper part”). Hereinafter referred to as black matrix) and the inside of the layer close to the back surface (hereinafter referred to as “photosensitive dark color composition layer lower part”, and black matrix also referred to as “black matrix lower part”). May go further. At this time, the lower part of the photosensitive dark color composition layer is in a dry state, and when the substrate on which the photosensitive dark color composition layer (black matrix) is formed is cut in the width direction of the black matrix, The shape of the composition layer is, for example, a reverse taper as shown in FIGS. Such a state is called a state with an undercut.
By providing an undercut in the photosensitive dark color composition layer, in a later step, the photosensitive coloring composition is placed on the black matrix on the substrate on which the black matrix is formed (hereinafter also referred to as “black matrix substrate”). When the colored pixels are provided so as to overlap with each other, the end portion in the width direction of the black matrix is deformed into an inclined surface as shown in FIG. That is, the inclination angle θ ₁ and the slope length of the inclined surface of the black matrix can be adjusted by the length of the undercut. In addition, the photosensitive dark color composition layer provided with the undercut may increase the length of the undercut in consideration of this because the length of the undercut may increase due to so-called thermal sag in the baking process described later. It is preferable to adjust.
In the photosensitive coloring composition, the slope length of the black matrix is 2.5 μm to 8 μm, the overlap length is 3 μm to 8 μm, and the inclination angle θ ₁ of the inclined surface of the black matrix is 10 ° ≦ θ ₁ <85 °. By applying and so on, the height of the horn is easily set to 0.5 μm or less. Therefore, the outer peripheral part of the colored pattern can be made difficult to rise. Thereby, when a color filter is manufactured and an image is displayed, disorder of liquid crystal alignment and light leakage can be suppressed, and a high-quality image can be obtained.
Hereinafter, the undercut will be described in more detail with reference to the drawings.

6 and 7 are cross-sectional views showing the black matrix substrate in a state in which the photosensitive dark color composition layer has an undercut.
As shown in FIG. 6, the length a of the undercut is the photosensitive dark color composition layer among the one end P in the width direction of the photosensitive dark color composition layer 4 and the lower part of the photosensitive dark color composition layer 4. 4 is a heel portion, and is obtained as a distance between the one end P and the portion Q farthest in the width direction.
In other words, the portion where the photosensitive dark color composition layer 4 is removed refers to the side surface where the photosensitive dark color composition layer 4 is removed.
Further, the portion farthest from the one end P in the width direction is not limited to the contact point between the surface of the photosensitive dark color composition layer 4 and the substrate 2 as shown in FIG. For example, as shown in FIG. 7, when an intermediate portion between the upper end (surface) and the lower end (bottom surface) in the thickness direction of the photosensitive dark color composition layer 4 is removed, the length a of the undercut is a. Is the distance from the one end P to the portion R of the photosensitive dark color composition layer 4 that is the farthest away from the one end P in the width direction.

As described above, from the viewpoint that the slope length of the black matrix is 2.5 μm to 8 μm and the inclination angle θ ₁ of the black matrix is 10 ° ≦ θ ₁ <85 °, the length of the undercut is 1.0 μm. It is preferably ˜8.0 μm. The shorter the undercut length, the shorter the slope length and the inclination angle θ ₁ becomes an obtuse angle. The longer the undercut length, the longer the slope length and the inclination angle θ ₁ becomes an acute angle. Although it depends on the conditions in other processes such as the thickness of the black matrix, exposure conditions, and pre-bake conditions, for example, the thickness of the black matrix is 0.8 μm to 1.2 μm, and the length of the undercut is In general, the slope length can be adjusted to 2.5 μm to 8.0 μm, and the inclination angle θ ₁ can be adjusted to 10 ° to 30 ° by setting the thickness to 1.0 to 5.0 μm.
The length of the undercut is preferably 1.0 μm to 8.0 μm, more preferably 1.5 μm to 7.0 μm, and most preferably 1.0 μm to 5.0 μm.
By setting the length of the undercut to 1.0 μm or more, the horn can be lowered and the liquid crystal display disorder of the color filter can be suppressed. Further, by setting the undercut to 8 μm or less, it is possible to prevent the end portion of the black matrix from being lost during development, and to prevent deterioration of the quality of the black matrix.
In addition, when the slope length is less than 2.5 μm, when forming colored pixels on the black matrix substrate, the overlapping portion is raised and the horn is increased, and when it exceeds 8.0 μm, During the operation after development of the photosensitive dark color composition layer, there arises a problem that the photosensitive dark color composition layer is missing or the photosensitive dark color composition layer is peeled off.

In order to make an undercut in the photosensitive dark color composition layer, it is important to appropriately adjust the development conditions, and the length of the undercut can be adjusted by changing the development conditions. The length of the undercut is also determined by the relationship with the constituent components of the black matrix, that is, the various components contained in the photosensitive dark color composition. Conceptually, when the photosensitive dark color composition is standard, the undercut amount can be increased as the development is performed under slightly stronger conditions than those normally used.
Stronger conditions include higher temperatures, longer times, higher flow rates, higher shower pressures, etc. Among them, temperature and time adjustments are particularly important.

Specifically, the development temperature is preferably 20 ° C. to 35 ° C., more preferably 23 ° C. to 30 ° C., from the viewpoint that the undercut can be accurately adjusted.
The development time is preferably from 30 seconds to 120 seconds, more preferably from 40 seconds to 90 seconds, from the viewpoint of easy undercutting.
Among these, a preferable combination of the development temperature and the development time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C. and 40 seconds to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably from 0.01 MPa to 0.5 MPa, preferably from 0.05 MPa to 0.3 MPa, and preferably from 0.1 MPa to 0.3 MPa from the viewpoint of preventing chipping of the black matrix.

  Moreover, in order to adjust the length of an undercut more finely, it is preferable to add the prebaking process mentioned later to a black matrix formation process. Although details will be described later, the undercut length can be increased as the pre-bake condition is weakened.

-Bake process-
Next, the black matrix pattern can be subjected to a heat treatment called baking (post-baking). Bake is a heat treatment after development for complete curing of the photosensitive dark color composition, and usually a heat curing treatment at 150 ° C. to 260 ° C. is performed.
The baking temperature is preferably 150 ° C to 260 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 ° C to 240 ° C. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 30 minutes to 90 minutes.
By baking the photosensitive dark color composition layer in the above condition range, when the colored pixels are formed on the substrate on which the black matrix is formed, the swell of the overlapping portion between the black matrix and the colored pattern is suppressed. Can do.

  The baking process is performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so that the photosensitive dark color composition layer after development is in the above-mentioned condition. It can be done with a formula.

-Other processes-
In the black matrix forming step in the present invention, a pre-baking step may be added after the photosensitive dark color composition layer forming step and before the exposing step, or after the developing step. Before the baking (post-baking) step, a step of curing the formed black matrix by exposure may be included if necessary.

(Pre-baking process)
As described above, in order to adjust the length of the undercut, it is preferable to appropriately adjust the pre-baking conditions in addition to adjusting the exposure and development conditions in the black matrix forming step. The black matrix formation step in the present invention is preferably performed at a lower temperature than the pre-bake conditions that are usually used.
Specifically, when prebaking with a hot plate, the prebaking temperature is preferably 65 ° C to 110 ° C. By setting the temperature to 65 ° C. or higher, it is possible to prevent the photosensitive dark color composition layer from being peeled off during the development process. By setting the temperature to 110 ° C. or lower, the lower portion of the photosensitive dark color composition layer is easily swallowed. Can be in a state. More preferably, it is 70 degreeC-100 degreeC, and 70 degreeC-90 degreeC is the most preferable. The pre-bake time is preferably 50 seconds to 300 seconds, more preferably 90 seconds to 200 seconds, and most preferably 100 seconds to 180 seconds. By performing pre-baking in the above condition range, it becomes easy to put an undercut in the photosensitive dark color composition layer.
By adjusting the length of the thus undercut it can be adjusted at the same time slopes length and the inclination angle theta _1.
In addition, prebaking can also be performed in an oven, and in this case as well, the length of the undercut can be adjusted by appropriately setting prebaking conditions equivalent to those described above.

[Colored pattern forming step]
In the present invention, the colored pattern is formed by forming a photosensitive colored composition layer using a photosensitive colored composition on a substrate on which a photosensitive dark colored composition layer (black matrix) after baking is formed (photosensitive). Photosensitive colored composition layer forming step), exposing the photosensitive colored composition layer (colored layer exposing step), developing the photosensitive colored composition layer after exposure (colored layer developing step), and developing It can be formed by baking the photosensitive coloring composition layer (colored layer baking step). In addition to the above steps, the coloring pattern forming step may further include other steps such as a pre-baking step as necessary.

In the color filter for a liquid crystal display element of the present invention, the slope length of the black matrix is 2.5 μm to 8 μm, and the overlap length is 3 μm to 8 μm.
The slope length and the overlap length can be adjusted by changing the exposure pattern position and development conditions of the photosensitive coloring composition layer.

Specifically, the amount of overlap can be reduced as the amount of overlap of the exposure pattern with the black matrix is reduced. The weaker the development conditions, for example, the lower the development temperature or the shorter the development time. The overlap amount can be increased as much as possible.
More specifically, in order to set the overlap length to 3 μm to 8 μm, it is preferable to set the distance between the exposure pattern and the black matrix to 3 μm to 8 μm. The development temperature is preferably 20 ° C to 35 ° C, more preferably 25 ° C to 35 ° C. Furthermore, the development time is preferably 20 seconds to 120 seconds, and more preferably 25 seconds to 70 seconds.

As a preferable combination of the above conditions, the distance between the exposure pattern and the black matrix is set to 3.0 μm to 8.0 μm, the development temperature is set to 20 to 35 ° C., and the development time is set to 20 seconds to 120 seconds. The combination is preferred.
A more preferable combination is a combination in which the distance between the exposure pattern and the black matrix is 3.0 to 7.0 μm, the development temperature is 25 ° C. to 30 ° C., and the development time is 30 seconds to 70 seconds. It is.

In the color filter for a liquid crystal display element of the present invention, the horn height of the colored pattern is required to be 0.5 μm or less.
The height of the horn can be adjusted by appropriately setting the above-described undercut length, overlap length, and black matrix thickness.

A preferable combination of the undercut length, the overlap length, and the film thickness of the black matrix is a length of the undercut from the viewpoint of reducing the horn and setting the optical density of the black matrix to 3.5 to 8.0. The thickness is preferably 1.0 μm to 7.0 μm, the overlap length is 3.0 μm to 7.0 μm, and the thickness of the black matrix is preferably 0.8 μm to 2.0 μm.
A more preferable combination is that the length of the undercut is 1.0 μm to 6.0 μm, the overlap length is 3.0 μm to 7.0 μm, and the thickness of the black matrix is 0.8 μm to 1. The thickness is 5 μm.
Next, various steps performed in the colored pattern forming step in the present invention will be described.

-Photosensitive coloring composition layer formation process-
In the photosensitive coloring composition layer forming step, the photosensitive coloring composition layer is formed using the photosensitive coloring composition on the substrate on which the photosensitive dark color composition layer (black matrix) after baking is formed. .
As a method for forming the photosensitive coloring composition layer on the substrate on which the black matrix is formed, a method similar to the method for forming the photosensitive dark composition layer on the substrate, that is, a coating method or a transfer method is used. be able to.
Especially, the method of apply | coating a photosensitive coloring composition to the board | substrate front surface in which the black matrix was formed with the slit coater etc. is preferable at the point which can show | play the effect of this invention well.
The layer thickness (for example, coating thickness) of the photosensitive coloring composition layer is preferably 0.5 μm to 3.0 μm in order to obtain a sufficient color reproduction region and sufficient panel luminance. More preferably, the thickness is 5 μm to 2.5 μm.

-Colored layer exposure process-
In the colored layer exposure step, the photosensitive colored composition layer is exposed.
The exposure treatment of the photosensitive coloring composition layer can be performed in the same manner as the exposure step of the photosensitive dark color composition layer. When forming a colored pattern of multiple colors, it is exposed for each color through a predetermined mask pattern of each color, and the photosensitive colored composition layer of each color irradiated with light is patterned (in the case of a negative type, it is cured) )can do.
For example, by adjusting the position of the mask pattern (distance between the photosensitive coloring composition layer and the mask pattern), the tangent line of the colored pattern and the light at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix The angle θ ₂ with the surface of the transparent substrate can be set to 5 ° ≦ θ ₂ <90 °. That is, by setting the position of the mask pattern close to the surface of the photosensitive coloring composition layer, the end of the photosensitive coloring composition layer is hardened and the angle θ ₂ tends to become an obtuse angle. On the other hand, by setting away the position of the mask pattern from the photosensitive coloring composition layer surface, for curing loose ends of the photosensitive coloring composition layer, the angle theta ₂ by development or the like after it tends to be an acute angle .
Furthermore, the magnitude of θ ₂ can also be adjusted by adjusting the degree of development and baking described later. For example, by increasing the shower pressure of the developer in the development process and developing the unexposed portion of the photosensitive coloring composition layer, the surface of the end portion of the photosensitive coloring composition layer is scraped to make the angle θ _{2 an} acute angle. I can do it.
Moreover, and surface cure initiator, by using appropriately adjusting the internal curing initiator, it is also possible to adjust the angle theta _2. The surface curable initiator is particularly preferably IRG907 (initiator manufactured by Ciba Specialty Chemicals), and the internal curable initiator is preferably a triazine-based initiator. For adjusting the angle θ ₂ , it is preferable to use an internally curable initiator.

-Colored layer development process-
In the colored layer developing step, the photosensitive colored composition layer after exposure is developed.
The development processing of the photosensitive coloring composition layer after the exposure can be performed in the same manner as described in the description of the development process of the photosensitive dark composition layer, and the developer described in the development process is preferable. Can be used.
As the development conditions, in order to adjust the overlap length and the height of the horn generated in the overlap portion between the black matrix and the colored pixels, the photosensitive coloring composition layer is formed under the development conditions described in the description of the overlap. It is preferable to develop.

-Colored layer baking process-
In the colored layer baking step, the developed photosensitive colored composition layer is baked.
The method for baking the photosensitive coloring composition layer after development can be the same method as the baking step for baking the photosensitive dark color composition layer described above.
When forming a colored pattern of a plurality of hues such as RGB three hues, the formation of the photosensitive coloring composition layer, exposure, development, and baking may be repeated for the desired number of hues, or for each hue. After the formation of the photosensitive coloring composition layer, exposure, and development, the entire hue may be finally baked. As a result, a color filter including a colored pixel having a black matrix and a desired hue is manufactured.

-Other processes-
Also in the colored pattern forming step, after the photosensitive colored composition layer forming step and before the colored layer exposing step, a step of pre-baking the photosensitive colored composition layer in order to dry the photosensitive colored composition ( A colored layer prebaking step) may be provided.
The pre-baking temperature of the photosensitive coloring composition layer is preferably 60 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The pre-bake time is preferably 30 seconds to 300 seconds, and more preferably 80 seconds to 200 seconds.

<Liquid crystal display device>
The color filter for a liquid crystal display element of the present invention is suitable for the production of a liquid crystal display device, and the liquid crystal display device manufactured using the color filter for a liquid crystal display element of the present invention can display a high-quality image. .
For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”.

The color filter for a liquid crystal display element of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. . These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".
In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter for a liquid crystal display element of the present invention can be applied to a liquid crystal display device composed of these known members.
For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, Ltd., issued by CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

In the present invention, it is preferable to have a photo spacer having an elastic modulus of 0.8 MPa to 3.0 MPa on the black matrix or the colored pattern formed on the black matrix.
When the elastic coefficient of the photo spacer is 0.8 MPa or more, uneven gravity due to the weight of the liquid crystal hardly occurs, and when the elastic coefficient of the photo spacer is 3.0 MPa or less, low-temperature firing is difficult to occur.
The elastic modulus of the photo spacer is particularly preferably 1.0 MPa to 1.5 MPa. As the photo spacer, a commercially available product can be used, and examples thereof include CSP-3210L (manufactured by FUJIFILM Corporation).

For the backlight, SID meeting Digest 1380 (200
5) (A. Konno et.al), Monthly Display, December 2005 issue 18
-24 pages (Yasuhiro Shima) and 25-30 pages (Takaaki Yagi).

  The color filter for a liquid crystal display element of the present invention can realize high contrast when combined with a conventionally known three-wavelength tube of a cold-cathode tube, but further backlights red, green and blue LED light sources (RGB-LED). Thus, a liquid crystal display device with high luminance and high color purity and good color reproducibility can be provided.

On the other hand, the performance required for the liquid crystal display device is to improve the response speed of the image. In order to improve the response speed, the liquid crystal alignment speed has been improved. On the other hand, from the structural aspect of the cell, it is necessary to reduce the thickness of the liquid crystal layer in terms of cost reduction. Another technique necessary for reducing the thickness of the liquid crystal layer is to reduce the alignment disorder of the liquid crystal at the boundary between the colored pixels and the black matrix. Therefore, it is required to reduce the bulge (horn) at the boundary between the colored pixel and the black matrix.
The color filter for a liquid crystal display element according to the present invention comprises: (I) an optical density of the black matrix of 3.5 to 8.0, and a film thickness of 0.8 μm to 2.0 μm; The horizontal distance from the shoulder to the lower end of the inclined surface at the end in the width direction is 2.5 μm to 8 μm; (III) The inclination angle θ ₁ of the inclined surface at the end in the width direction of the frame of the black matrix is 10 ° ≦ θ ₁ <85 °; (IV) The horizontal distance between the outer peripheral line of the colored pattern overlapping the frame and the lower end of the inclined surface is 3 μm to 8 μm; (V) The film thickness of the colored pattern is 1.5 μm. ~2.5μm; (VI) wherein the angle between the tangent line and the light transmitting substrate of the surface of the colored pattern in that the peripheral line of the colored pattern overlaps the surface of the black matrix theta ₂ is, 5 ° ≦ θ ₂ <90 °; (VII) contained in the photosensitive coloring composition Among the pigments, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% of the total amount of the pigment, and the proportion of the pigment having a primary particle size of more than 0.08 μm By making it less than 5% in the total amount, (VIII) the difference in height between the flat surface of the central portion of the colored pattern and the maximum raised portion of the outer peripheral portion of the colored pattern (the height of the horn) is reduced, that is, 0.5 μm. It can be as follows.

  As described above, since the color filter for a liquid crystal display element of the present invention has small horns, it is possible to reduce the disorder of the alignment of the liquid crystal in the overlap portion, and the visibility when displaying an image is improved. By using the color filter of the present invention in the liquid crystal display device of the present invention, the overlapping portion of each colored pixel with the black matrix can be flattened, and when the flatness is good, the liquid crystal layer can be made thin. In addition, it is not necessary to polish or provide a flattening layer before laying a transparent electrode (for example, ITO), which can contribute to streamlining of processes and cost reduction and mass productivity.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight. “Wt%” represents “mass%”.

Example 1
<1. Preparation of photosensitive dark color composition>
-Preparation of carbon black dispersion (K-1)-
A carbon black dispersion (K-1) was prepared according to the following formulation.
・ Carbon black (Color Black FW2 manufactured by Degussa) ・ ・ 26.7 parts ・ Dispersant (Dispalon DA7500 manufactured by Enomoto Kasei Co., Ltd., acid value 26, amine value 40)
... 3.3 parts benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) copolymer (molecular weight 30,000, 50 mass% solution of propylene glycol monomethyl ether acetate) ... 10 parts propylene Glycol monomethyl ether acetate 60 parts

  The above components were stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain a carbon black dispersion (K-1). It was.

  Using the obtained carbon black dispersion liquid (K-1), a photosensitive dark color composition coating liquid CK-1 was prepared according to the formulation shown in Table 1 below. Numerical values in Table 1 indicate mass ratios.

Details of each component in Table 1 are as follows.
Resin solution C-2: benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (Mw 10,000, 50 wt% solution of propylene glycol monomethyl ether acetate)
UV curable resin C-3: trade name Cyclomer P ACA-250 manufactured by Daicel Chemical Industries, Ltd. [Acrylic copolymer having alicyclic, COOH, and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate Solution (solid content: 50% by mass)]
Polymerizable compound C-5: trade name TO-1382 manufactured by Toagosei Co., Ltd. (The main component is a monomer having a pentafunctional acryloyl group in which part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group. )
・ Initiator C-7: Trade name “OXE-02” Ciba Specialty Chemicals Co., Ltd. ・ Surfactant C-8: Trade name “Megafac R30” Dainippon Ink & Chemicals, Inc. ・ Solvent: PGMEA = Propylene glycol monomethyl ether acetate EEP = 3-Ethoxyethyl propionate

<2. Formation of black matrix>
-Photosensitive dark color composition layer forming step-
Using the obtained photosensitive dark color composition CK-1 on a glass substrate (Corning Millennium 0.7 mm thickness) using a slit coater (model number HC6000, manufactured by Hirata Kiko Co., Ltd.), the film thickness after post-baking is The distance between the slit and the glass substrate was set to 150 μm so that the thickness (1.2 μm) shown in the black matrix column of Table 7 below was obtained, and the ejection amount was adjusted, and coating was performed at a coating speed of 120 mm / second.

-Pre-bake process, exposure process-
Next, after heating (prebaking treatment) at 90 ° C. for 120 seconds using a hot plate, exposure is performed at 100 mJ / cm ² using a mirror projection type exposure machine (model number MPA-8000, manufactured by Canon Inc.). did.

-Development process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0% developer (CDK-1 by 1 part by mass) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) The black matrix after development was obtained by setting the shower pressure to 0.20 MPa with 99 parts by mass of pure water diluted at 25 ° C., developing for 50 seconds, and washing with pure water. Here, the length of the undercut was measured by taking a cross-sectional photograph with an SEM and found to be 5 μm.
SEM imaging was performed by cutting the black matrix together with the substrate in the width direction of the black matrix and perpendicular to the substrate surface in the vicinity of the center of the long side of the black matrix.

-Bake (post-bake) process-
Next, a post-baking process is performed in a clean oven at 240 ° C. for 40 minutes, and a black pixel substrate having a color pixel formation area of 90 μm × 200 μm, a black matrix thickness of 1.2 μm, and a black matrix line width of about 22 μm. Formed.
Using X-Rite 361T (V) (manufactured by Sakata Inx Engineering Co., Ltd.)
The optical density (OD) of the finished black matrix was measured and found to be 4.2.

<Production of color filter>
-Photosensitive coloring composition layer formation process-
(Preparation of pigment dispersion 1)
Pigment dispersion 1 was prepared as follows. That is, with the composition shown in Table 2 below, the mixture was stirred for 3 hours at a rotation speed of 3,000 rpm using a homogenizer to prepare a mixed solution, and further 0.1 mmφ zirconia beads were used. Dispersion treatment was carried out for 8 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries).

Details of the components in Table 2 are as follows.
・ C. I. Pigment Red254
CROMOPHTAL RED BP made by Ciba Specialty Chemicals
[Pigment in which R in general formula (A) is a chlorine atom]
・ Disperbic 161
Manufactured by Big Chemie [30% by mass solution was used. Therefore, the solid content is 2.1 parts. ]
・ PEGMEA
Propylene glycol methyl ether acetate

(Preparation of photosensitive coloring composition CR-1)
Components of the composition shown in Table 3 below were further added to the obtained pigment dispersion 1 (240 parts), and the mixture was stirred and mixed to prepare a red (R) photosensitive coloring composition coating liquid CR-1.

Details of the components in Table 3 are as follows.
・ BZMA / MMA
Copolymer of benzyl methacrylate and methacrylic acid (= 70/30 [molar ratio]) Weight average molecular weight = 30,000
・ DPHA
Dipentaerythritol hexaacrylate / 1-methoxy-2-propyl acetate (76/24 [mass ratio]) manufactured by Nippon Kayaku Co., Ltd., “KAYARAD DPHA”]
・ LD5
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (“B-CIM” manufactured by Hodogaya Scientific Co., Ltd.)
・ Triazine initiator 1
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine)
・ Epicron N695
“Epicron 695” manufactured by Dainippon Ink & Chemicals, Inc.
・ PEGMEA / EPA
Propylene glycol methyl ether acetate and 3-ethoxyethyl propionate (= 80/20 [mass ratio]) mixed solution / surfactant 1
Made by Dainippon Ink & Chemicals, MegaFuck F-780-F

About the pigment in photosensitive coloring composition coating liquid CR-1, "the primary particle diameter exceeds 0.08 micrometer" with respect to the total solid of photosensitive coloring composition coating liquid CR-1, and "the primary particle diameter is 0. The ratio of “pigment less than 0.02 μm” was determined as follows.
That is, the pigment powder was observed with a transmission electron microscope (TEM), the TEM photograph was subjected to image analysis, the particle size distribution was examined, and the primary particle size was determined. Specifically, the total number of particles in the observation sample at a magnification of 100,000, and the number of pigment particles less than 0.02 μm and more than 0.08 μm were measured.
For primary particle size, the proportion of primary particles less than 0.02 μm, the proportion of primary particles greater than 0.08 μm is determined by measuring the major axis of each primary particle, and particles of pigments less than 0.02 μm and greater than 0.08 μm The ratio (number%) of was calculated. The pigment powder was observed with a transmission electron microscope at a magnification of 3 to 100,000 times, a photograph was taken, the major axis of 1000 primary particles was measured, and the ratio of primary particles of less than 0.02 μm and more than 0.08 μm was calculated. . When this operation was performed for a total of three locations with different pigment powder locations, and the results were averaged, the ratio of “pigments with a primary particle diameter exceeding 0.08 μm” was 0.50% (number distribution). The ratio of “pigment having a primary particle diameter of less than 0.02 μm” was 1.6% (number distribution).

(Photosensitive coloring composition layer formation)-
The obtained red (R) photosensitive coloring composition coating liquid CR-1 was applied to the black matrix forming surface side of the black matrix substrate. Specifically, as in the case of forming the photosensitive dark color composition layer, the layer thickness of the photosensitive coloring composition layer after post-baking is the thickness (2.0 μm) shown in the color filter column of Table 7. In this way, the gap between the slit and the black matrix substrate and the discharge amount were adjusted, and coating was performed at a coating speed of 120 mm / second.

-Colored layer pre-baking step, colored layer exposure step-
Next, after heating (pre-baking treatment) at 100 ° C. for 120 seconds using a hot plate, exposure was performed at 90 mJ / cm ² using a proximity exposure machine (manufactured by Hitachi High-Tech, LE5565A).
Further, the mask pattern and the exposure machine were set so that the overlap (exposure overlap amount) between the exposure pattern and the black matrix was 8.0 μm.

-Colored layer development process, colored layer baking (post-baking) process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0% developer (CDK-1 by 1 part by mass) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) The shower pressure was set to 0.2 MPa with 99 parts by mass of pure water diluted at 25 ° C., developed for 45 seconds, and washed with pure water.
Next, post-baking was performed in a 220 ° C. clean oven for 30 minutes to form heat-treated red pixels.

When the SEM cross-sectional photograph of 10 pixels selected at random was taken and the slope length and overlap length of the black matrix were measured, the arithmetic averages were 5 μm and 5 μm, respectively.
The SEM cross-sectional photograph was taken in the width direction of the black matrix in the vicinity of the center of the long side of the black matrix and was taken by SEM.
In addition, when the height of “Tsun” of 100 randomly selected colored patterns was measured using a contact type surface roughness meter P-10 (manufactured by KLA Tencor), the arithmetic average was 0. .28 μm. As shown in FIG. 8, the height of the horn was measured by moving the stylus 12 in the width direction (A direction) of the black matrix 10 in the vicinity of the center of the lattice long side of the black matrix 10.
Further, the height of the horn formed by the pixels of each color and the black matrix was determined as the difference between the height of the flat surface at the center of the colored pattern and the maximum raised portion of the outer periphery of the colored pattern.

Further, from the SEM cross-sectional photograph of 10 pixels selected at random, the “inclination angle θ ₁ of the inclined surface at the end in the width direction of the black matrix” and the “peripheral line of the colored pattern overlap the surface of the black matrix. When the angle θ ₂ between the tangent of the colored pattern at the point and the surface of the light-transmitting substrate was measured, the arithmetic average was 30 ° for θ ₁ and 45 ° for θ ₂ .

<Production of liquid crystal display device>
An ITO (Indium Tin Oxide) transparent electrode was further formed by sputtering on the R pixel of the color filter obtained above and the black matrix. Separately, a glass substrate was prepared as a counter substrate, and an ITO transparent electrode was similarly formed by sputtering. A columnar photospacer obtained through the following formation process (columnar photospacer formation 1) is provided in a portion corresponding to the upper part of the partition on the ITO transparent electrode, and an alignment film made of polyimide is further provided thereon. It was.

-Formation of columnar photo spacer-
(Synthesis of Resin [Compound P-1])
7.48 parts of 1-methoxy-2-propanol (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance to the reaction vessel, the temperature was raised to 90 ° C., and ADMA (manufactured by Hitachi Chemical Co., Ltd.) 6.35. A mixed solution consisting of 0.26 parts of methacrylic acid, 3.62 parts of methacrylic acid, 0.22 parts of azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 7.48 parts of 1-methoxy-2-propanol It was dripped over 2 hours in 90 degreeC reaction container under gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, 0.020 part of hydroquinone monomethyl ether and 0.46 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 3.53 parts of glycidyl methacrylate was added dropwise over 2 hours. After dripping, after reacting at 90 ° C. for 4 hours while blowing air, a resin solution of compound P-1 having the following structure having an unsaturated group was prepared by adding a solvent so that the solid concentration was 45%. (Solid acid value: 70.6 mg KOH / g, Mw: 30,000, 1-methoxy-2-propanol 45% solution) (polymerization ratio 41.0 mol%: 24.0 mol%: 35.0 mol%) .

  The molecular weight Mw of compound P-1 was measured by gel permeation chromatography (GPC). For GPC, HLC-8020GPC (manufactured by Tosoh Corporation) is used, TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns, and THF (tetrahydrofuran) is used as an eluent. ) Was used. The conditions were as follows: the sample concentration was 0.35 / min, the flow rate was 0.35 ml / min, the sample injection amount was 10 μl, the measurement temperature was 40 ° C., and an IR detector was used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It produced from eight samples of "A-2500", "A-1000", and "n-propylbenzene".

(Formation of photo spacer)
On the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced as described above was sputtered, a glass substrate coater MH-1600 (manufactured by FAS Asia Co., Ltd.) having a slit-like nozzle was used. A photosensitive resin layer coating solution having the formulation shown in FIG. Subsequently, after part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove the fluidity of the coating film, it was pre-baked at 120 ° C. for 3 minutes, and the film thickness was 4.5 μm. A functional resin layer was formed.

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Technologies Corporation) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. Proximity exposure with the distance between the mask surface and the surface of the photosensitive resin layer set to 40 μm with the arranged color filter substrate standing substantially parallel and vertically and an exposure amount of 100 mJ / cm ² through the mask did.

  Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Containing agent: Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, and shower-developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. An image was formed. Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) diluted 10 times with pure water And sprayed with a shower at a cone type nozzle pressure of 0.02 MPa at 33 ° C. for 20 seconds to remove residues around the formed pattern image, and a cylindrical spacer pattern was formed on a black matrix with a size of 300 μm × 300 μm. It formed so that it might become a spacer interval of a book.

Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 230 ° C. for 30 minutes, thereby producing a photo spacer on the color filter substrate. Here, 1000 photo spacers obtained were measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) to measure the highest position of the highest spacer from the ITO transparent electrode forming surface side ( n = 20), and the average value when averaged was defined as the average height. Moreover, the measurement of the bottom area of the obtained photospacer was performed using the SEM photograph. As a result, it was a cylindrical shape having a diameter of 24 μm and an average height of 4.3 μm.

-Formation of liquid crystal alignment split projections-
A coating liquid for photosensitive resin layer for protrusions having the following formulation A was applied onto the ITO transparent electrode on the color filter by the same slit coater as described above and dried to form a photosensitive resin layer for protrusions.

<Coating liquid for photosensitive resin layer for protrusions: Formulation A>
-Positive resist solution: 53.3 parts [FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.]
・ Methyl ethyl ketone 46.7 parts ・ Surfactant 2 below 0.04 parts

(Surfactant 2)
・ The following structure 1 ・ ・ ・ 30%
・ Methyl ethyl ketone 70%

Subsequently, it exposed at 150 mJ / cm < ² > using the mirror projection system exposure machine (model number MPA-8000, Canon Inc. make).
Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying on the photosensitive resin layer for protrusions at 33 ° C. for 30 seconds in a shower type developing device, and an unnecessary portion (exposure) of the photosensitive resin layer for protrusions was exposed. Part) was developed and removed. Then, protrusions patterned in a desired shape were formed on the ITO transparent electrode of the color filter above the R pixel. Next, the color filter substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes, so that a height of 1.5 μm and a longitudinal sectional shape (a surface parallel to the normal direction of the glass substrate surface) are formed on the color filter. It was possible to form alignment-dividing protrusions having a shape).

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to a black matrix outer frame provided so as to surround the colored pixel group of the color filter, and MVA mode liquid crystal is dropped to form a counter substrate. After the substrates were bonded together and irradiated with UV, the sealant was cured by heat treatment. A liquid crystal cell was thus obtained. A polarizing plate HLC2-2518 (manufactured by Sanritz Co., Ltd.) was pasted on both sides of this liquid crystal cell, and then placed on the back surface side of the liquid crystal cell provided with the polarizing plate by constituting a backlight of a cold cathode tube, A liquid crystal display device was obtained.

-Image quality evaluation of liquid crystal display devices-
The liquid crystal display device was energized and various display images were visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 7 below.
<Evaluation criteria>
○: There is no unevenness, and the display feels vivid and powerful.
Δ: There is no unevenness, but the display does not feel forceful ×: There is unevenness or it looks whitish, and it cannot endure viewing.

-Evaluation of contrast-
Light that has passed through the other polarizing plate with light applied from the side of one polarizing plate in a state where the polarizing plates are overlapped on both surfaces of the glass substrate on which the colored pattern is formed and the polarizing directions of the polarizing plates are parallel to each other The luminance (luminance when parallel) was measured. Next, in a state where the polarizing plates were orthogonal to each other, light was applied from the side of one polarizing plate, and the luminance of light passing through the other polarizing plate (luminance at the time of orthogonality) was measured. A value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for contrast evaluation. Here, Nitto Denko G1220DUN was used as the polarizing plate, and a color luminance meter BM-5 (manufactured by Topcon Corporation) was used as the measuring instrument.
The results are shown in Table 7 below.
<Evaluation criteria>
○: Value is 6,000 or more Δ: Value is 4,000 or more and less than 6,000 ×: Value is less than 4,000

(Examples 2 to 6, Example 9, and Examples 13 to 19)
In the production of the liquid crystal display device of Example 1, Examples 2 to 6, Example 9, and Example 13 were performed in the same manner as Example 1 except that the production conditions were changed to the conditions shown in Table 6 below. A liquid crystal display device of Example 19 was produced and evaluated in the same manner as in Example 1.
In Table 6, CK-3 and CK-4 are the photosensitive dark color composition coating liquids CK-3 and CK-4 shown in Table 1. In Table 6, CK-2 was prepared as follows.

-Preparation of photosensitive dark color composition coating liquid CK-2-
The pigment dispersion K-2 and propylene glycol monomethyl ether acetate in the amounts shown in Table 5 below are weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. However, the amounts of methyl ethyl ketone, cyclohexanone, binder 2, phenothiazine, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisdiethoxycarbonylmethyl) amino shown in Table 5 3′-bromophenyl] -s-triazine and the surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.), and 150 r.p. at a temperature of 40 ° C. (± 2 ° C.). by stirring for 30 minutes at m.
A photosensitive dark color composition coating solution CK-2 was obtained.

In addition, the quantity of the said Table 5 is a mass part, and the detail of each component is as showing below. (Pigment dispersion K-2)
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (Compound 1 below) 0.65%
・ Polymer 6.72%
[Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio,
Molecular weight 37,000]
Propylene glycol monomethyl ether acetate 79.53%

(Binder 2)
・ Polymer ・ ・ ・ 27%
[Random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio,
Molecular weight 38,000]
・ Propylene glycol monomethyl ether acetate 73%

(DPHA solution)
・ Dipentaerythritol hexaacrylate: 76%
[Polymerization inhibitor MEHQ 500ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA]
・ Propylene glycol monomethyl ether acetate: 24%

(Example 7, Example 8)
In the production of the liquid crystal display device of Example 1, the production conditions were changed to those shown in Table 6 below, and in the colored layer exposure step, Example 7 had an exposure amount of 60 mJ / cm ² and Example 8 had an exposure amount. The liquid crystal display devices of Examples 7 and 8 were produced in the same manner as in Example 1 except that the value was changed to 120 mJ / cm ² , and evaluated in the same manner as in Example 1.

(Example 10)
In the formation of the color filter of Example 1, the production conditions were changed to the conditions shown in Table 6 below, and a blue (B) photosensitive coloring composition layer was formed using the photosensitive coloring composition coating liquid CB-1. A color filter of Example 10 was formed in the same manner except that the colored layer exposure step was changed to the following step.
That is, it exposed at 90 mJ / cm < ² > using the proximity exposure machine (The Hitachi High-Tech make, LE5565A). At this time, a strip-shaped exposure pattern extending in the longitudinal direction of the black matrix is used, and in the width direction of the exposure pattern, a mask pattern and an exposure pattern are overlapped with the black matrix (exposure overlap amount) to 8.0 μm. An exposure machine was set up. By setting and exposing in this way, the blue (B) photosensitive coloring composition layer formed on the black matrix in the longitudinal direction of the black matrix was exposed and cured.

Next, in the production of the liquid crystal display device of Example 1, the columnar photo spacer was disposed and formed so as to be positioned on the blue (B) photosensitive coloring composition layer formed on the black matrix. The liquid crystal display device of Example 10 was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
In addition, the photosensitive coloring composition coating liquid CB-1 was prepared as follows.

-Preparation of photosensitive coloring composition coating liquid CB-1-
(Preparation of blue pigment dispersion B1)
In the preparation of the pigment dispersion 1, a pigment (CI Pigment Red254; CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals) I. Pigment Blue 15: 6, and the dispersion treatment time was changed from 8 hours to 3 hours, in the same manner as in the preparation of Pigment Dispersion Liquid 1, to obtain a pigment dispersion B1 for blue.

(Preparation of photosensitive coloring composition coating solution CB-1)
Photosensitive coloring composition coating liquid CR-1 was prepared in the same manner as in the preparation of photosensitive coloring composition coating liquid CR-1, except that blue pigment dispersion B1 was used instead of pigment dispersion 1. A colored composition coating liquid CB-1 was obtained.

(Example 11, Example 12)
In the production of the liquid crystal display device of Example 1, the liquid crystal display devices of Examples 11 and 12 were produced in the same manner as in Example 1 except that the production conditions were changed to those shown in Table 6 below. Evaluation was performed in the same manner as in Example 1.
In Table 6 below, photosensitive coloring composition coating solutions CR-3 and CR-4 were prepared as follows.

-Synthetic examples of polymer compounds having a heterocyclic ring in the side chain-
(Synthesis of polymer 1)
M-11 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (new The mixture is stirred with Toshin Kagaku Co., Ltd .: Three-One Motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. Moreover, the acid value per solid content was 98 mgKOH / g from the titration using sodium hydroxide.

(Synthesis of polymer 2)
M-6 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The temperature is increased to 90 ° C. by stirring while flowing nitrogen in the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. From the titration with sodium hydroxide, the acid value per solid content was 99 mgKOH / g.

(Preparation of coated pigment 1)
50 g of pigment (CI Pigment Red254, CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals), 500 g of sodium chloride, 20 g of the above-described polymer 1 solution, and 100 g of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. Kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

(Preparation of coated pigment 2)
In preparation of the coated pigment 1, C.I. I. Pigment Green 36 (Monastral Green 6Y-CL manufactured by Nippon Lubrizol Co., Ltd.), Polymer 2 was used instead of Polymer 1, and the coating pigment 2 was prepared in the same manner as the coating pigment 1 except for the above.

(Evaluation of pigment coverage)
10 g of the obtained pigment was put into 100 mL of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was precipitated with a centrifugal separator at 80,000 rpm for 8 hours. The solid content of the supernatant was determined from the drying method. The amount of the polymer compound released from the pigment was determined, and the release rate (%) was calculated from the ratio with the polymer compound used in the treatment. The smaller the liberation rate, the higher the degree of coverage on the pigment.
Both of the coated pigments 1 and 2 obtained above showed a free amount of 20% by mass or less, and were found to be coated pigments.

-Preparation of photosensitive coloring composition coating liquid CR-3-
(Preparation of pigment dispersion 3)
In the preparation of Pigment Dispersion Liquid 1, instead of 35 parts of pigment (CROMOPHTAL RED BP manufactured by C.I. Pigment Red254 Ciba Specialty Chemicals), the pigment dispersion liquid is used except that 35 parts of the coated pigment 1 is used in an amount corresponding to the pigment. In the same manner as in the preparation of 1, a pigment dispersion 3 was obtained.

(Preparation of photosensitive coloring composition coating liquid CR-3)
Components of the following composition were further added to the obtained pigment dispersion 3 and mixed by stirring to prepare a photosensitive coloring composition coating liquid CR-3.
・ Alkali-soluble resin: copolymer of benzyl methacrylate and methacrylic acid (= 70/30 [molar ratio]) Weight average molecular weight = 30,000 19.8 parts ・ Monomer: DPHA 20 parts, Nippon Kayaku Co., Ltd. ・ Start of polymerization Agent: 3,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 3 parts-polymerization initiator: 4- [o-bromo-pN, N-di ( Ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 3 parts, diethylaminobenzophenone 0.5 part, N-phenylmercaptobenzimidazole 0.5 part, polyfunctional epoxy compound: Dainippon Ink Chemical 5 parts of Epicron 695 manufactured by Kogyo Co., Ltd. Surfactant: 1.0 part of surfactant 1 Solvent (propylene glycol methyl ether acetate / 3 Ethoxyethyl propionate = 8/2) 400 parts of

-Preparation of photosensitive coloring composition coating liquid CR-4-
(Preparation of pigment dispersion 4)
A pigment dispersion 4 was obtained in the same manner as the pigment dispersion 3, except that 35 parts of the coating pigment 2 was used instead of the coating pigment 1 in preparation of the pigment dispersion 3.

(Preparation of photosensitive coloring composition coating liquid CR-4)
In the preparation of the photosensitive coloring composition coating liquid CR-3, the photosensitive coloring composition was prepared in the same manner as the photosensitive coloring composition coating liquid CR-3 except that the pigment dispersion liquid 4 was used instead of the pigment dispersion liquid 3. A product coating solution CR-4 was obtained.

(Example 20)
In the production of the liquid crystal display device of Example 1, a black matrix was prepared in the same manner as in Example 1 except that the photosensitive coloring composition coating liquid CG-1 was used instead of the photosensitive coloring composition coating liquid CR-1. A green (G) photosensitive coloring composition layer was formed thereon, then a liquid crystal display device of Example 20 was produced and evaluated in the same manner as in Example 1.
In Table 6, CG-1 used in Example 20 was prepared as follows.

-Preparation of photosensitive coloring composition coating liquid CG-1-
(Preparation of green pigment dispersion G1)
In the preparation of the pigment dispersion 1, a pigment (CI Pigment Red254; CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals) I. Pigment Green 7 (manufactured by BASF, HELIOGEN GREEN D8730) was used, and the dispersion treatment time was changed to 12 hours, and a pigment dispersion G1 for green color was obtained in the same manner as the pigment dispersion 1.

(Preparation of photosensitive coloring composition coating solution CG-1)
Photosensitive coloring composition coating liquid CR-1 was prepared in the same manner as in the preparation of photosensitive coloring composition coating liquid CR-1, except that green pigment dispersion G1 was used instead of pigment dispersion 1. A colored composition coating liquid CG-1 was obtained.

Example 21
In the production of the liquid crystal display device of Example 2, the black matrix was formed so that the film thickness after post-baking of the black matrix was the thickness (1.4 μm) shown in Table 7 below. Then, a liquid crystal display device of Example 21 was produced and evaluated in the same manner as in Example 2.

[Comparative Example 1]
In the production of the liquid crystal display device of Example 1, the heating temperature in the pre-baking process in forming the black matrix was changed from 90 ° C. to 120 ° C., and the shower pressure in the developing process was changed from 0.20 MPa to 1.0 Mpa, Further, a liquid crystal display device was produced in the same manner as in Example 1 except that the development time was changed from 50 seconds to 40 seconds. Moreover, it evaluated similarly to Example 1. FIG.

[Comparative Examples 2 to 5]
In the production of the liquid crystal display device of Example 1, the liquid crystal display devices of Comparative Examples 2 to 5 were produced in the same manner as in Example 1 except that the production conditions were changed to those shown in Table 6 below. Evaluation was performed in the same manner as in Example 1.
In Table 6, CR-2 used in Comparative Example 2 was prepared as follows.

-Preparation of photosensitive coloring composition coating liquid CR-2-
A pigment dispersion 2 was obtained in the same manner as in the preparation of the pigment dispersion 1, except that the dispersion for 8 hours in the preparation of the pigment dispersion 1 was changed to 3 hours. A photosensitive coloring composition coating liquid CR-2 was prepared in the same manner as in the preparation of the photosensitive coloring composition coating liquid CR-1, except that the pigment dispersion liquid 1 was changed to the pigment dispersion liquid 2.

[Comparative Example 6]
In the production of the liquid crystal display device of Example 1, the photosensitive dark color composition coating liquid CK-1 was changed to the photosensitive dark color composition coating liquid CK-5 having the following composition, and the film thickness after the post-baking of the black matrix. The liquid crystal display device of Comparative Example 6 was prepared in the same manner as in Example 1 except that the black matrix was formed so that the thickness of the liquid crystal display device was 1.2 μm and the production conditions of the liquid crystal display device were changed to the conditions shown in Table 6 below. This was prepared and evaluated in the same manner as in Example 1.

-Preparation of photosensitive dark color composition coating liquid CK-5-
[Preparation of carbon black dispersion (K-5)]
The carbon black dispersion (K-5) was prepared in the same manner as in the preparation of the carbon black dispersion (K-1) except that 26.7 parts of carbon black (Color Black FW2 manufactured by Degussa) were changed to 19.0 parts. ) Was prepared.

[Preparation of photosensitive dark color composition coating solution CK-5]
In the same manner as in the preparation of the photosensitive dark color composition coating liquid CK-1, except that the carbon black dispersion liquid (K-1) was changed to the carbon black dispersion liquid (K-5), the photosensitive dark color composition was used. A coating solution CK-5 was prepared.

[Comparative Example 7]
In the production of the liquid crystal display device of Example 1, the photosensitive dark color composition coating liquid CK-1 was changed to the photosensitive dark color composition coating liquid CK-6 having the following composition, and the film thickness after the post-baking of the black matrix. The liquid crystal display device of Comparative Example 7 was manufactured in the same manner as in Example 1 except that the black matrix was formed so as to be 2.4 μm and the manufacturing conditions of the liquid crystal display device were changed to the conditions shown in Table 6 below. This was prepared and evaluated in the same manner as in Example 1.

-Preparation of photosensitive dark color composition coating liquid CK-6-
[Preparation of carbon black dispersion (K-6)]
The carbon black dispersion (K-6) was prepared in the same manner as in the preparation of the carbon black dispersion (K-1) except that 26.7 parts of carbon black (color black FW2 manufactured by Degussa) were changed to 13.4 parts. ) Was prepared.

[Preparation of photosensitive dark color composition coating solution CK-6]
In the same manner as in the preparation of the photosensitive dark color composition coating liquid CK-1, except that the carbon black dispersion liquid (K-1) was changed to the carbon black dispersion liquid (K-6), the photosensitive dark color composition was used. A coating solution CK-6 was prepared.

[Comparative Example 8]
In the production of the liquid crystal display device of Example 1, the photosensitive dark color composition coating solution 1 was subjected to an exposure amount of a colored pattern of 40 mJ / cm ² using a proximity exposure machine (model number LE5565A, manufactured by Hitachi High-Tech). In the same manner as in Example 1 except that the colored pattern was formed so that the overlap length was 2 μm and the production conditions were changed to the conditions shown in Table 6 below. A liquid crystal display device was produced and evaluated in the same manner as in Example 1.

[Comparative Example 9]
In the production of the liquid crystal display device of Example 1, the photosensitive dark color composition coating liquid 1 was subjected to a color pattern exposure of 150 mJ / cm ² using a proximity exposure machine (model number LE5565A, manufactured by Hitachi High-Tech). In the same manner as in Example 1, except that the colored pattern was formed so that the overlap length was 8 μm and the production conditions were changed to the conditions shown in Table 6 below. A liquid crystal display device was produced and evaluated in the same manner as in Example 1.

[Comparative Example 10]
In the production of the liquid crystal display device of Example 1, the shower pressure in the colored layer development step was changed to 0.1 MPa, the development time was changed to 30 seconds to form red pixels, and the production conditions were as shown in Table 6 below. A liquid crystal display device of Comparative Example 10 was produced in the same manner as in Example 1 except that it was changed, and evaluated in the same manner as in Example 1.

[Comparative Example 11]
In the production of the liquid crystal display device of Example 1, the photosensitive coloring composition coating liquid CR-1 was changed to the photosensitive coloring composition coating liquid CR-5 having the following composition, and the photosensitive coloring composition layer after post-baking was used. In the same manner as in Example 1, except that the photosensitive coloring composition layer was formed so that the layer thickness was about 3.0 μm, and the production conditions of the liquid crystal display device were changed to the conditions shown in Table 6 below. A liquid crystal display device of Example 11 was produced and evaluated in the same manner as in Example 1.

-Preparation of photosensitive coloring composition coating liquid CR-5-
(Preparation of pigment dispersion 5)
Preparation of Pigment Dispersion Liquid 1 was the same as the preparation of Pigment Dispersion Liquid 1 except that 35 parts of pigment (CI Pigment Red254; CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals) was changed to 23.4 parts. Thus, a pigment dispersion 5 was obtained.

(Preparation of photosensitive coloring composition coating liquid CR-5)
In the preparation of the photosensitive coloring composition coating liquid CR-1, the photosensitive coloring composition was prepared in the same manner as in the preparation of the photosensitive coloring composition coating liquid CR-1, except that the pigment dispersion liquid 5 was used instead of the pigment dispersion liquid 1. A product coating solution CR-5 was obtained.

[Comparative Example 12]
In the production of the liquid crystal display device of Example 1, a comparison was made in the same manner as in Example 1 except that the photosensitive coloring composition coating liquid CR-1 was changed to the photosensitive coloring composition coating liquid CR-6 having the following composition. A liquid crystal display device of Example 11 was produced and evaluated in the same manner as in Example 1.

-Preparation of photosensitive coloring composition coating liquid CR-6-
(Preparation of pigment dispersion 6)
A pigment dispersion 6 was obtained in the same manner as in the preparation of the pigment dispersion 1, except that the dispersion treatment time was changed from 8 hours to 10 hours in the preparation of the pigment dispersion 1.
As for the pigment in the obtained pigment dispersion 6, a TEM photograph was taken and the particle size distribution was examined by image analysis. As a result, 13.4% of particles having a particle size of less than 0.02 μm and 0.2 particle having a particle size exceeding 0.08 μm were 0.2. %Met.

(Preparation of photosensitive coloring composition coating liquid CR-6)
In the preparation of the photosensitive coloring composition coating liquid CR-1, a photosensitive coloring composition was prepared in the same manner as in the preparation of the photosensitive coloring composition coating liquid CR-1, except that the pigment dispersion liquid 6 was used instead of the pigment dispersion liquid 1. A product coating solution CR-6 was obtained.

[Comparative Example 13]
In the production of the liquid crystal display device of Example 2, the black matrix was formed so that the film thickness after post-baking of the black matrix was the thickness (1.6 μm) shown in Table 7 below. Then, a liquid crystal display device of Comparative Example 13 was produced and evaluated in the same manner as in Example 2.

  In Table 6, the unit of time is “second”, and the unit of temperature is “° C.”. Further, “over 0.08 μm” in the “pigment ratio” column means that the primary particle diameter in the total amount of pigment in the photosensitive coloring composition used in Examples 1-21 or Comparative Examples 1-13 is 0.00. The ratio (%) of the pigment exceeding 08 μm, and “less than 0.02 μm” means the primary particle diameter in the total amount of the pigment in the photosensitive coloring composition used in Examples 1 to 21 or Comparative Examples 1 to 13 Is the proportion (%) of pigments less than 0.02 μm.

In Table 7, the units of film thickness, line width, undercut, slope length, overlap length, and horn height are all “μm”. The film thickness in the color filter column refers to the film thickness of the colored pattern.
In Table 7, “on BM” in the position column of the photo spacer indicates that the photo spacer is formed on the black matrix (BM), and “on BM / BLUE” indicates that the photo spacer is black. It shows that it is formed on the blue photosensitive coloring composition layer (BLUE) formed on the matrix (BM).

  As can be seen from Table 7, the height of the horn was suppressed in the color filters of the examples, and it was found that the liquid crystal display device using these color filters had high quality image quality.

  In Comparative Example 13, chipping occurred in the photosensitive dark color composition layer after development of the photosensitive dark color composition layer in forming the black matrix. Further, in the color filter formed in Comparative Example 13, as shown in FIG. 5, the outer peripheral line of the coloring pattern did not reach the top surface of the black matrix, and was positioned in the middle of the inclined surface of the black matrix.

2 Light transmitting substrate 4 Black matrix frame (black matrix, photosensitive dark color composition layer)
6 Coloring pattern (photosensitive coloring composition layer)
8 Overlap part 9 Slope part

Claims (7)

On a light-transmitting substrate, a black matrix formed using a photosensitive dark color composition, and a colored pattern formed using a photosensitive coloring composition between the slopes defined by the black matrix, ,
The optical density of the black matrix is 3.5 to 8.0, and the film thickness is 0.8 μm to 2.0 μm;
The horizontal distance from the shoulder to the lower end of the inclined surface at the end in the width direction of the black matrix frame is 2.5 μm to 8 μm;
The inclination angle θ ₁ of the inclined surface at the end in the width direction of the black matrix frame is 10 ° ≦ θ ₁ <85 °;
A horizontal distance between the outer peripheral line of the colored pattern overlapping the frame and the lower end of the inclined surface is 3 μm to 8 μm;
A film thickness of the colored pattern is 1.5 μm to 2.5 μm;
The angle θ ₂ between the tangent of the colored pattern and the surface of the light transmissive substrate at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix is 5 ° ≦ θ ₂ <90 °;
Of the pigments contained in the photosensitive coloring composition, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% in the total amount of the pigment, and the primary particle size is 0.08 μm. The proportion of pigment exceeding is less than 5% of the total amount of the pigment;
A color filter for a liquid crystal display element, wherein a difference in height between a flat surface at a central portion of the colored pattern and a maximum raised portion of an outer peripheral portion of the colored pattern is 0.5 μm or less.   The color filter for a liquid crystal display element according to claim 1, wherein the pigment is a pigment coated with a resin. The pigment is a compound represented by the following general formula (A), C.I. I. Pigment green 36, or C.I. I. The color filter for a liquid crystal display element according to claim 1, wherein the color filter is a pigment green 7.


In [Formula (A), R represents a hydrogen atom, a methyl group, an ethyl group, a propyl _{group, -N (CH 3) 2,} -N (C 2 H 5) 2, -CF 3, chlorine atom, or Represents a bromine atom. ]   The photo spacer having an elastic coefficient of 0.8 MPa to 3.0 MPa is provided on the black matrix or a colored pattern formed on the black matrix. The color filter for liquid crystal display elements of item 1. The inclination angle θ ₁ of the inclined surface at the end in the width direction of the frame of the black matrix is 10 ° ≦ θ ₁ ≦ 60 °, and
The angle θ ₂ between the tangent of the colored pattern and the surface of the light-transmitting substrate at the point where the outer peripheral line of the colored pattern overlaps the surface of the black matrix is 5 ° ≦ θ ₂ ≦ 80 °. The color filter for liquid crystal display elements according to any one of claims 1 to 4.   Furthermore, the color filter for liquid crystal display elements of any one of Claims 1-5 which have a transparent electrode.   The color filter for a liquid crystal display element according to claim 1, wherein a width of the black matrix frame is 15 μm to 30 μm.