JP2009244774A - Color filter substrate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter substrate which suppresses display unevenness by stabilizing the cell gap of a liquid crystal display even when reducing the line width of a black matrix to achieve a high aperture ratio, and a liquid crystal display including the same. <P>SOLUTION: The color filter substrate including the black matrix and a photospacer satisfies relation of Kb≤Kp, wherein Kb(μm) is the amount of deformation to load of the black matrix and Kp(μm) is that of the photospacer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a color filter substrate and a liquid crystal display device.

  Liquid crystal display devices are widely used in display devices that display high-quality images. In a liquid crystal display device, a liquid crystal layer capable of displaying an image with a predetermined orientation is generally disposed between a pair of substrates (hereinafter also referred to as a “display device substrate”). Maintaining uniformity is one of the factors that determine image quality, and for this purpose, a spacer is provided to keep the thickness of the liquid crystal layer constant. The thickness between the substrates is generally referred to as “cell thickness or cell gap”, and the cell thickness is usually the thickness of the liquid crystal layer, in other words, between two electrodes applying an electric field to the liquid crystal in the display region. Indicates distance.

  A color filter substrate as a display device substrate has a structure in which a colored pattern and a structure such as a black matrix are formed around the substrate. Among these structures, a method of forming a colored pattern or a black matrix by photolithography using a photosensitive resin composition has become the mainstream.

  In addition, spacers have conventionally been formed by bead dispersion, but in recent years, spacers with high positional accuracy have been formed by photolithography using a photosensitive resin composition. A spacer formed using such a photosensitive resin composition is called a photospacer.

By the way, in the color filter substrate, if the line width of the black matrix is narrowed for the purpose of high aperture ratio, the area of the photo spacer must be reduced accordingly, so a hard photo spacer is selected to maintain strength. (For example, Patent Document 1)
JP 2004-212929 A

  However, if a hard photo spacer is simply selected, a hardness imbalance between the black matrix and the photo spacer occurs, and the cell gap cannot be stabilized, resulting in display unevenness.

  Accordingly, the present invention provides a color filter substrate capable of stabilizing the cell gap of a stable liquid crystal display device and suppressing display unevenness even when the line width of the black matrix is reduced in order to achieve a high aperture ratio, An object of the present invention is to provide a liquid crystal display device including the same.

The above problem is solved by the following means. That is, the present invention
<1> In a color filter substrate having a black matrix and a photo spacer,
A color filter substrate satisfying a relationship of Kb ≦ Kp, where Kb (μm) is a deformation amount against load of the black matrix and Kp (μm) is a deformation amount against load of the photo spacer.
<2> The color filter substrate according to <1>, wherein the relationship of the following formulas (1) and (2) is satisfied.
Formula (1): y ₁ ≦ Kb ≦ y ₂ (where y ₁ = 0.001x + 0.05, y ₂ = 0.001x + 0.15),
Formula (2): y ₃ ≦ Kp ≦ y ₄ (where y ₃ = 0.006x + 0.15, y ₄ = 0.006x + 0.25)
(Formula (1) and (2) in, x is the applied load; indicates _mN, y 1 ~y ₄ is the deformation versus load; [mu] m shown.)
<3> The color filter substrate according to <1> or <2>, wherein the black matrix has a line width of 30 μm or less.
<4> The color filter substrate according to any one of <1> to <3>, wherein an equivalent circle diameter of the photospacer is 25 μm or less.
<5> A liquid crystal display device comprising the color filter substrate according to any one of <1> to <4>.

  According to the present invention, a color filter substrate capable of stabilizing the cell gap of a stable liquid crystal display device and suppressing display unevenness even when the line width of the black matrix is reduced in order to achieve a high aperture ratio, And a liquid crystal display device including the same can be provided.

<Color filter substrate>
The color filter substrate of the present invention is a color filter substrate having a black matrix and a photo spacer. Specifically, the color filter substrate of the present invention includes, for example, two or more patterned colored pixels (hereinafter referred to as a colored pattern) formed on the substrate and having different hues, and the color filter substrate. A black matrix and a photo spacer formed on the black matrix are provided around the periphery. A transparent conductive layer (transparent electrode) such as ITO and an alignment film such as polyimide may exist between the black matrix and the photo spacer.

  In the color filter substrate of the present invention, the relationship of Kb ≦ Kp is satisfied when the amount of deformation of the black matrix against load is Kb (μm) and the amount of deformation of the photo spacer against load is Kp (μm). In this way, by setting the hardness balance between the black matrix and the photo spacer to the above predetermined relationship, even if the line width of the black matrix is narrowed in order to achieve a high aperture ratio, a stable cell gap of the liquid crystal display device is achieved. Can be stabilized and display unevenness can be suppressed.

  In addition, the amount of deformation against load of the black matrix and the photospacer can be controlled, for example, by adjusting the composition of the resin composition forming them and the baking treatment.

In the color filter substrate of the present invention, it is preferable that the relationship of the following formulas (1) and (2) is further satisfied.
Formula (1): y ₁ ≦ Kb ≦ y ₂ (where y ₁ = 0.001x + 0.05, y ₂ = 0.001x + 0.15),
Formula (2): y ₃ ≦ Kp ≦ y ₄ (where y ₃ = 0.006x + 0.15, y ₄ = 0.006x + 0.25)
(Formula (1) and (2) in, x is the applied load; indicates _mN, y 1 ~y ₄ is the deformation versus load; [mu] m shown.)

  This equation (1) means that the black matrix has a relatively small amount of deformation with respect to the load, and further, the equation (2) has a relatively large amount of deformation of the photo spacer with respect to the load. Means. Therefore, by satisfying the relationship of the above formulas (1) and (2), the cell gap of a stable liquid crystal display device can be achieved even if the line width of the black matrix is reduced more effectively in order to achieve a high aperture ratio. Can be stabilized and display unevenness can be suppressed.

  Here, the load deformation amount is a value measured by a micro hardness meter (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement is performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm and a holding time of 5 seconds. The amount of deformation at the time of the load is defined as the amount of deformation against load.

  The load load (mN) can be set arbitrarily within the range that can be output from the measuring device. However, when the load load is 5 mN or less, the error becomes large and is not appropriate. When it is 500 mN or more, there is a possibility that physical destruction of the resist may occur, which is not realistic. Therefore, it is good to set to the said range.

  The color filter substrate of the present invention will be described in more detail together with its manufacturing method. The color filter substrate of the present invention includes, for example, a black matrix forming step, a colored pattern forming step, and a photo spacer forming step, and can be configured by further providing other steps as necessary.

  Hereinafter, the black matrix forming process, the colored pattern forming process, and the photo spacer forming process will be described separately.

[Black matrix formation process]
In the present invention, in the black matrix forming step, at least a photosensitive dark color composition layer is formed on a substrate using the photosensitive dark color composition (photosensitive dark color composition layer forming step), and the photosensitive dark color composition is formed. A color composition layer is exposed (exposure process), the photosensitive dark color composition layer after the exposure is developed (development process), and an undercut length of 3.0 to 8.0 μm is a black matrix pattern And the black matrix pattern thus formed is baked (baking step) to form a black matrix. In addition to the above steps, the black matrix forming step may be provided with other steps as necessary.

-Black matrix-
In the present invention, the black matrix preferably has an optical density (OD value) of 2.0 or more and 8.0 or less, more preferably 3.0 or more, and still more preferably 4.0 to 6.0. When the optical density is 2.0 or more, deterioration of display quality of the display device such as suppression of reduction of contrast can be suppressed.
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.
Further, the black matrix preferably has a line width (length in a direction perpendicular to the longitudinal direction of the black matrix sandwiched between the colored patterns) of 30 μm or less, more preferably from the viewpoint of ensuring brightness by increasing the aperture ratio. Is 27.5-5 μm, more preferably 25-7.5 μm. And even if the black matrix line width is narrowed to achieve a high aperture ratio as in the above range, the cell gap of a stable liquid crystal display device is stabilized and display unevenness is suppressed. be able to.
The thickness of the black matrix (the length of the black matrix in the normal direction of the substrate) is from the viewpoint of reducing the bulge of the overlapping portion where the black matrix and the colored pattern overlap (preferably 0.5 μm or less). 2-2.0 micrometers is preferable, More preferably, it is 0.2-1.5 micrometers, More preferably, it is 0.5-1.2 micrometers. Within this thickness range, 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. Even when formed on top, it can be formed with high accuracy.

-Photosensitive dark color composition layer forming step-
In this step, a photosensitive dark color composition layer is formed on the substrate using the photosensitive dark color composition.
Examples of substrates that can be used in this step include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, solid-state imaging devices, and the like. For example, a photoelectric conversion element substrate, such as a silicon substrate, may be used. Furthermore, a plastic substrate is also possible. Among these, alkali-free glass is preferable from the viewpoint of chemical resistance and heat resistance. 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. When performing the above-described various coatings, it is preferable from the viewpoint of improving coating properties to clean the substrate with ultraviolet rays or various cleaning liquids before performing these coatings.
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, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 are used. It can be suitably used in the present invention.
As a laminator used for transfer, FIG. A laminator described in No. 24 or a laminator described in International Application No. JP2007 / 069312 can be suitably used. High productivity can be obtained by using these laminators.

  The thickness (for example, coating thickness) when the photosensitive dark color composition is applied onto the substrate is appropriately adjusted depending on the design value of the thickness of the black matrix to be formed, but is generally 0.2-2. 0.2 μm is preferable, 0.2 to 1.6 μm is more preferable, and 0.5 to 1.3 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 5~500mJ / cm ^2, more preferably 10 to 300 mJ / cm ^2, and most preferably 10~200mJ / cm ^2.
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 present invention, the black matrix pattern is formed so that the undercut length is 3.0 to 8.0 μm after the main development process and before the baking process described later. 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 (black matrix), a photosensitive coloring composition is formed on a substrate on which the black matrix is formed (hereinafter also referred to as “black matrix substrate”) in a later step. When a colored pixel is provided by applying an object or the like, the boundary portion between the black matrix and the colored pixel can be made difficult to rise. Thereby, when a color filter is produced 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.

1 and 2 are cross-sectional views showing a black matrix substrate in a state where an undercut is present in the black matrix (photosensitive dark color composition layer).
As shown in FIG. 1, 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 portion where there is no photosensitive dark color composition, and the distance between the end P and the portion Q farthest in the width direction is obtained. 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. 2, 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.

The length of the undercut is preferably 3.0 to 8.0 μm, and from the viewpoint of reducing the rise of the overlap portion where the black matrix and the colored pixels overlap (preferably 0.50 μm or less), 3.5-8.0 micrometers is more preferable, 4.0-8.0 micrometers is further more preferable, 4.0-7.0 micrometers is especially preferable, and 4.0-6.0 micrometers is the most preferable.
When the undercut length is in the above range, when forming colored pixels on the black matrix substrate, it is possible to effectively suppress the bulge of the overlap portion, and a photosensitive dark color composition such as a baking step described later. During the operation after the development of the physical layer, the photosensitive dark color composition layer is chipped or the photosensitive dark color composition layer can be effectively prevented from peeling off. From the viewpoint of reducing the black matrix line width and undercut developer temperature dependency (from the viewpoint of systematically forming the black matrix), the undercut length is preferably in the range of 3.0 to 5.0.

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. Conceptually, the amount of undercut can be increased as the development is performed under conditions that are slightly stronger than the development conditions that are commonly 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 to 35 ° C, more preferably 25 to 30 ° C, from the viewpoint that the undercut can be adjusted with high accuracy.
The development time is preferably from 30 to 120 seconds, more preferably from 40 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 to 100 seconds at a temperature of 25 ° C. and 40 to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably from 0.01 to 0.5 MPa, preferably from 0.05 to 0.3 MPa, and preferably from 0.1 to 0.3 MPa, from the point that BM chipping can be prevented.

  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 is 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 to 260 ° C. is performed.
The baking temperature is preferably 150 to 260 ° C, more preferably 180 to 260 ° C, and most preferably 200 to 240 ° C. The baking time is preferably 10 to 150 minutes, more preferably 20 to 120 minutes, and most preferably 30 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 rise of the overlap portion between the black matrix and the colored pixels is suppressed. Can do.

  The baking process is carried out 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 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 to 120 ° 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. Can be in a state. More preferably, it is 70-100 degreeC, and 70-90 degreeC is the most preferable. The pre-bake time is preferably 50 to 300 seconds, more preferably 90 to 200 seconds, and most preferably 100 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.
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 colored pattern forming step, at least a photosensitive colored composition layer is formed using a photosensitive colored composition on a substrate on which a photosensitive dark color 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 By baking the photosensitive coloring composition layer (colored layer baking step), the colored pattern is such that the distance in the black matrix width direction of the overlapped portion overlapping the black matrix after baking is 1.0 to 12 μm. Form. In addition to the above steps, the coloring pattern forming step may further include other steps such as a pre-baking step as necessary.

First, the “overlap” will be described.
-Overlap-
When a photosensitive coloring composition is applied on a substrate on which a black matrix is formed to form a colored pattern (colored pixels), photosensitive coloring is performed so that no gap is formed between the black matrix and the colored pixels. It is common to form a colored pixel by slightly covering (overlapping) the photosensitive coloring composition with the black matrix so that the composition and the black matrix overlap. In the present invention, a high-quality color filter or liquid crystal display device can be obtained by adjusting the distance of the overlap portion to 1.0 to 12 μm in addition to the above-described undercut.
The “distance of the overlap portion” refers to the distance in the black matrix width direction of the overlap portion where the color pattern formed using the photosensitive coloring composition layer and the black matrix overlap. This will be described in more detail with reference to the drawings.

FIG. 3 shows a case where a photosensitive coloring composition layer 6 is formed on a substrate 2 on which a black matrix 4 is formed by applying a photosensitive coloring composition to form the black matrix 4 and the photosensitive coloring composition layer 6. It is a fragmentary sectional view of the color filter which shows the state in which the overlap part 8 which overlapped was formed. Here, the overlap portion 8 is a region of distance b, and the distance b of the overlap portion 8 is the outermost end S on the side facing the photosensitive coloring composition layer 6 in the width direction of the black matrix 4; It can be determined as the distance in the width direction of the black matrix 4 between the photosensitive coloring composition layer 6 provided so as to overlap the black matrix 4 and the outermost end T located on the black matrix 4.
Actually, the distance b of the overlap portion 8 can be obtained by cutting the color filter in a direction perpendicular to the longitudinal direction of the pattern of the black matrix 4 and measuring from the cross section.

The distance of the overlap portion should be 1.0 to 12 μm, preferably 1.0 to 10 μm, from the viewpoint of reducing the rise of the overlap portion (preferably 0.50 μm or less). 0.0 to 8.0 μm is more preferable, and 2.0 to 6.0 μm is most preferable.
Further, by setting the distance of the overlap portion to 12 μm or less, it is possible to stably manufacture the color filter and the display device on a large substrate (one side of 1 m or more).

The overlap distance can be adjusted by changing the exposure pattern position of the photosensitive coloring composition layer and the development conditions. 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 portion distance to 1.0 to 12 μm, it is preferable to set the distance between the exposure pattern and the black matrix to 1.0 to 12 μm. The development temperature is preferably 20 to 35 ° C, and more preferably 25 to 35 ° C. Furthermore, the development time is preferably 20 to 120 seconds, and more preferably 25 to 70 seconds.

A preferable combination of the above conditions is a combination in which the distance between the exposure pattern and the black matrix is 2.0 to 12 μm, the development temperature is 20 to 35 ° C., and the development time is 20 to 120 seconds. 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 9.0 μm, the development temperature is 25 to 30 ° C., and the development time is 30 to 70 seconds. .

  As described above, in the overlap portion between the black matrix and the photosensitive coloring composition layer, the photosensitive coloring composition is covered with the black matrix so that the black matrix and the photosensitive coloring composition layer partially overlap each other. , That part will be raised. By reducing the degree of the bulge of the overlap portion, it is possible to suppress disorder of liquid crystal alignment and light leakage, and a high quality image can be obtained. The rise of the overlap portion will be described with reference to the drawings.

FIG. 4 shows that a photosensitive coloring composition layer is formed by applying a photosensitive coloring composition on the substrate 2 on which the black matrix 4 is formed, and is exposed and developed to form a coloring pattern 6. 4 is a partial cross-sectional view of a color filter showing a state in which a bulge is generated in an overlap portion 8 where 4 and a colored pattern 6 overlap.
More specifically, the “degree of swell of the overlap portion” means the surface of the substrate 2 of the overlap portion 8 (the surface of the substrate 2 in contact with the black matrix 4 or the color pattern 6 among the surfaces of the color pattern 6). ) And the distance in the normal line of the substrate between the portion farthest from the substrate and the flat surface portion other than the overlap portion 8. In other words, the “degree of swell of the overlap portion” is the normal line of the substrate between the surface of the substrate 2 and the portion of the surface of the colored pattern 6 that is farthest from the surface of the substrate 2 of the overlap portion 8. The distance e is obtained by subtracting the distance d at the normal line of the substrate between the surface of the substrate 2 and the portion of the surface of the colored pattern 6 other than the overlap portion 8 from the distance c.

Hereinafter, the rise of the overlap portion will be referred to as “horn” for the sake of convenience, and the distance e will be referred to as “horn height”. The height of the horn is preferably 0.5 μm or less, more preferably 0.4 μm or less, and most preferably 0.25 μm or less in terms of obtaining a high-quality image.
The height of the horn can be adjusted by appropriately setting the above-described undercut length, the distance of the overlap portion, and the thickness of the black matrix.

A preferable combination of the length of the undercut, the distance of the overlap portion, and the thickness of the black matrix is such that the length of the undercut is 3.5 to 7.5 μm, and the distance of the overlap portion is 1.5. It is preferable that the thickness of the black matrix is 0.2 to 1.5 μm. A more preferable combination is that the length of the undercut is 4.0 to 6.0 μm, the distance of the overlap portion is 2.5 to 8.5 μm, and the thickness of the black matrix is 0.5 to 1 .2 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.
Among them, the method of applying the photosensitive coloring composition to the front surface of the substrate on which the black matrix is formed with a slit coater or the like is preferable because the effects of the present invention can be exhibited well.
The layer thickness of the photosensitive coloring composition layer is preferably 0.5 to 3.0 μm in order to obtain a sufficient color reproduction region and sufficient panel luminance, and in the range of 1.0 to 2.5 μm. More preferably.

-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.

-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 distance of the overlap portion and the height of the horn generated in the overlap portion between the black matrix and the colored pixels, the photosensitive coloring composition is used under the development conditions described in the description of the overlap. It is preferred to develop the layer.

-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.
60-140 degreeC is preferable and, as for the prebaking temperature of the photosensitive coloring composition layer, 80-120 degreeC is more preferable. The pre-bake time is preferably 30 to 300 seconds, more preferably 80 to 200 seconds.

[Photo spacer formation process]
The photo-spacer forming step is performed after the black matrix forming step and the colored pattern forming step, and after forming a transparent conductive layer (transparent electrode) such as ITO and an alignment film such as polyimide as necessary. A step of forming a film of the photosensitive resin composition on the finished substrate (hereinafter also referred to as “film formation step”) and a step of exposing at least a part of the film (hereinafter also referred to as “exposure step”). And a step of developing the coated film after exposure (hereinafter also referred to as “developing step”), and a step of heating the coated film as necessary (hereinafter referred to as “film baking process”). Or other steps may be provided.

  Here, the equivalent circle diameter of the photospacer is preferably 25 μm or less, more preferably 22.5 to 5 μm, and most preferably 20 to 7.5 μm. Even if the photoequivalent circle diameter of the photo spacer is within the above range and the photoequivalent circle diameter of the photo spacer is reduced to achieve a high aperture ratio, the cell gap of the stable liquid crystal display device is stabilized and display unevenness is suppressed. be able to.

-Film formation process-
In the film forming step, a film of the photosensitive resin composition is formed on the substrate. As a method for forming a photosensitive resin layer on a substrate, (a) a coating method in which a photosensitive resin composition containing at least the above-described resin, polymerizable compound, and photopolymerization initiator is applied, and (b) the above-mentioned A transfer method in which a photosensitive transfer material having a photosensitive resin layer is used, and the photosensitive resin layer is laminated and transferred by heating and / or pressurization is preferable.

(A) Application method The photosensitive resin composition is applied by a known application method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, or wire bar coating. , Gravure coating, or extrusion coating using a popper described in US Pat. No. 2,681,294. Among them, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A, A method using a slit nozzle or a slit coater described in JP 2001-310147 A is suitable.

(B) Transfer method Transfer is performed using a photosensitive transfer material, for example, a roller or flat plate in which a photosensitive resin layer formed in a film shape on a temporary support is heated and / or pressed on a desired substrate surface. Then, the photosensitive resin layer is transferred onto the substrate by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

In the case of forming the photosensitive resin layer, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) can be further provided between the photosensitive resin layer and the temporary support. Thereby, exposure sensitivity can be improved. In order to improve transferability, a thermoplastic resin layer having cushioning properties may be provided.
Paragraph numbers [0024] to [0024] of Japanese Patent Application Laid-Open No. 2006-23696 describe the temporary support, the oxygen-blocking layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer material and the method for producing the photosensitive transfer material. The structure and manufacturing method described in [0030] can be applied.

  When the photosensitive resin layer is formed by both the coating method (a) and the transfer method (b), the layer thickness is preferably 0.5 to 10.0 μm, and more preferably 1 to 6 μm. When the layer thickness is in the above range, the generation of pinholes during the formation of coating during production is prevented, and development and removal of unexposed portions can be performed without requiring a long time.

  Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), a substrate with a color filter (also referred to as a color filter substrate), and the like. Examples thereof include a drive substrate with a drive element (for example, a thin film transistor [TFT]). The thickness of the substrate is generally preferably 700 to 1200 μm.

-Exposure process and development process-
In the exposure step, at least a part of the coating formed in the coating formation step is exposed to form a latent image. In the subsequent development step, the coating film exposed in the exposure step can be developed to form a spacer pattern having a desired shape.

  Specific examples of these processes include the formation examples described in paragraphs [0071] to [0077] of JP-A-2006-64921, and paragraph numbers [0040] to [0051] of JP-A-2006-23696. The process described in 1 can be given as a suitable example in the present invention.

Here, although a film baking process described later may be provided, the cross-sectional shape is uniform without providing a film baking process (hereinafter also referred to as “no heating process”) by increasing the exposure amount in the exposure. It is also possible to form a photospacer excellent in uniformity and height.
By setting “no heating process”, it is possible to more effectively suppress the deterioration of the photo spacer to be formed and the deterioration of the already formed pattern structure (colored pattern, etc.) and protective film.
The exposure amount at which a "no heating step" is preferably 1 to 500 mJ / cm ^2, preferably 10 to 300 mJ / cm ^2.

-Coating bag-
A film baking process for heating the film after development in the development process can also be provided. By heating, curing of the film is further promoted, and a photospacer having high strength is obtained. Moreover, when the resin in the photosensitive resin composition has a branched and / or alicyclic structure in the side chain, a photospacer having a good compression modulus and elastic recovery can be obtained.

Here, although the maximum temperature in a bag (heating) changes with heating time, it is preferable that it is 40 to 145 degreeC, and it is more preferable that it is 40 to 140 degreeC. When the maximum temperature is within a range of 40 ° C. to 145 ° C., the deterioration of the photo spacer to be formed, and the deterioration of the already formed pattern structure (colored pattern, etc.) and protective film are more effectively suppressed. it can.
Especially, it is more preferable that the maximum temperature in heating is 80 ° C. to 140 ° C., and the heating time is 0.1 hour to 3.0 hours (more preferably 0.2 hour to 1.0 hour).

  Next, the photosensitive coloring composition, photosensitive dark color composition, and photosensitive resin composition used in the method for producing a color filter of the present invention will be described 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) a binder polymer, (C-1) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Other additives such as a dispersant and a surfactant may be included.

-(A-1) Colorant-
As the colorant, a dye / pigment system can be appropriately selected. The pigment used as the colorant may be an inorganic pigment or an organic pigment, but preferably has a high transmittance. In view of the above, it is preferable to use one having a particle size as small as possible. The average particle size is preferably 10 to 100 nm, more preferably 10 to 50 nm. 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.

  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
Etc.

Although it does not specifically limit in this invention, The following pigment is more preferable.
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, 254, 255, 264;
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), an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or A mixture with a perylene-based 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 diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, 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 preferably 25 to 75% by mass with respect to the total solid content (mass) of the composition. 32 to 70% by 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.

-(B) Binder polymer-
The photosensitive coloring composition of the present invention preferably contains a binder polymer for the purpose of improving film properties and imparting development properties. The following alkali-soluble resins can be used as the binder polymer.
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 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, and more preferably 50 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 already described, the acrylic resin has an acid value in the range of 20 to 200 mgKOH / g. When the acid value is 200 or less, it is possible to prevent the acrylic resin from being excessively soluble in alkali and narrowing the appropriate development range (development latitude). On the other hand, if it is 20 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 .; Biscort 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) And UCB 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-10
59, YDF-8170, YDF-170 etc. (above, manufactured by Toto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 etc. (above, produced by Nagase Kasei Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical Industries, Ltd.) and the like, and bisphenol F type and bisphenol S type epoxy resins similar to these can also be mentioned. .

Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (above, manufactured by Daicel UC Corporation) 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 Tohto Kasei Co., Ltd.), Denacol EM-125, etc. The biphenyl type is 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-based 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, for the compatibility and dispersibility with other components (for example, binder polymer, initiator, colorant (pigment, dye, etc.) in the photosensitive coloring composition layer, the selection and use method of the addition polymerization compound is as follows. For example, compatibility may be improved by using a low-purity compound or using two or more compounds in combination, and selecting a specific structure for the purpose of improving adhesion to the substrate. There is also a possibility.

  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 mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha) are preferred.

  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) Manufactured) is more preferable.

  (C-1) The content of the polymerizable compound is preferably 5 to 55% by mass and preferably 10 to 50% by mass in the total solid content in the photosensitive coloring composition layer of the present invention. More preferably, it is 15-45 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 phenylketone, 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 Forinophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4 -Acetophenone derivatives such as morpholinobyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples thereof include benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate 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) biidazole, 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. Publications, JP 2000-131837 A, JP 2002-107916 A, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, 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 No. 61-166544 and Japanese Patent Application No. 2001-132318.

  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, 4,069,056, phosphonium salts described in European Patent Nos. 104,143, U.S. Pat. Nos. 339,049, 410,201. And iodonium salts described in JP-A-2-150848 and JP-A-2-296514.

  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. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

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. No. 4,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013 No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604 Examples thereof include sulfonium salts described in each specification of No. 581. From the viewpoint of stability, 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 preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more 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 compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 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, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  (D) It is preferable that content of a photoinitiator is 0.1-20 mass% with respect to the total solid in a photosensitive coloring composition layer, More preferably, it is 0.5-15 mass%, Especially it is. Preferably it is 1-10 mass%. 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 20-300 mg / 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 be obtained by copolymerizing a vinyl monomer 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.

Moreover, it is also preferable to contain the group which has a basic nitrogen atom for a dispersibility improvement. 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 (polyester) manufactured by Lubrizol Corporation Amine), 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. , M YS-IEX (polyoxyethylene monostearate) ”and the like.

  The above-mentioned known dispersants can be used in the range of 10 to 100% by mass, that is, 1/10 to 1/1 (equivalent) with respect to the dispersion resin as necessary.

(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, Adeka Pluronic series, Adecanol series i, Tetronic series (above ADEKA Co., Ltd.), Emulgen series, Rheodor series (above Kao Co., Ltd.), Eleminor series, Nonipol Series, Octapole series, Dodecapole series, New Pole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.), etc. is there. 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 GE Toshiba Silicone Co., Ltd.).

  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 order to promote alkali solubility of the uncured portion and further improve the developability of the photocurable composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. be able to. 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.
When the silane coupling agent is used, the addition amount is preferably in the range of 0.2 to 5.0% by mass in the total solid content in the photosensitive coloring composition layer used in the present invention. 5-3.0 mass% is 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 in the range of 0.1 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. Preferably, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

(Polymerization inhibitor)
In the present invention, a small amount of a thermal polymerization inhibitor is added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during 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 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 contains (A-2) a light-shielding agent, (B) a binder polymer, (C-2) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Preferably, other additives such as a dispersant and a surfactant can be contained as required.

-(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). Of these, carbon black is particularly preferred because of its excellent balance between light shielding properties and cost.
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, X, T, and G 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 color composition used for forming the black matrix is 5 to 50% by mass in the total solid content of the photosensitive dark color composition layer. Preferably, it is 7-40 mass%, More preferably, it is 10-35 mass%.

  The (B) binder polymer, (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 preferred content is also the same.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention has a 5-membered or 6-membered cyclic structure containing a site represented by C═O and / or P═O in the side chain [A], an acidic group, In addition, a resin having an ethylenically unsaturated bond, [B] a polymerizable compound, and [C] a photopolymerization initiator is preferably included. Of course, the photosensitive resin composition of the present invention is not limited to the above configuration, but by using the above configuration, the curability at the time of exposure is improved, and the pattern structure can be formed without a low heating temperature or heat treatment. It becomes possible. For this reason, it is possible to effectively suppress the deterioration of the pattern structure to be formed and the deterioration of the pattern structure already formed on the substrate. Therefore, the photosensitive resin composition of the present invention is applied not only to a photospacer but also to the photosensitive colored resin composition for forming a colored pattern and the photosensitive dark color resin composition for forming a black matrix. May be.

Hereinafter, each component which comprises the photosensitive resin composition of this invention is demonstrated in detail.
[A] Resin The photosensitive resin composition of the present invention has a 5-membered or 6-membered cyclic structure or acidic group containing a site represented by C═O and / or a site represented by P═O in the side chain. And at least one resin having an ethylenically unsaturated bond.
Since this resin has a 5-membered or 6-membered cyclic structure including a site represented by C═O and / or a site represented by P═O in the side chain, the curability during exposure is improved.
In addition, this resin has an acidic group and developability, and also has an ethylenically unsaturated bond, so that it has high polymerization reactivity and is excellent in liquid storage and storage over time in a dry film. Therefore, it is possible to impart controllability that allows the pattern structure to be controlled to have a desired shape and a required film thickness (height, etc.).
Moreover, when it has a branched and / or alicyclic structure so that it may mention later, the compression elastic modulus at the time of receiving the external force of the formed pattern structure and the elastic recoverability from a compressive deformation can be improved. Thus, it is useful for constructing a pattern structure such as a color filter spacer.

  Here, the 5-membered or 6-membered cyclic structure, the acidic group, and the ethylenically unsaturated bond including the site represented by C═O and / or the site represented by P═O are in different side chains. May be contained in the same side chain, or all of them may be contained in the same side chain.

  In the present specification, (meth) acryloyl group represents acryloyl group or methacryloyl group, (meth) acrylate represents acrylate or methacrylate, (meth) acryl represents acryl or methacryl, and (meth) acrylamide represents acrylamide. Alternatively, it represents methacrylamide, and (meth) acrylanilide represents acrylanilide or methacrylanilide.

~~ 5-membered or 6-membered cyclic structure containing a site represented by C = O and / or a site represented by P = O ~
[A] The resin has a 5-membered or 6-membered cyclic structure containing a moiety represented by C═O and / or a moiety represented by P═O in the side chain bonded to the main chain of the resin (hereinafter referred to as “ At least one kind of “specific cyclic structure”. A plurality of specific cyclic structures may be included in the side chain of [A] resin. Moreover, the specific cyclic structure may be contained in the side chain of [A] resin with an acidic group and / or an ethylenically unsaturated bond.
Further, the specific cyclic structure may be directly bonded to the main chain of the [A] resin to constitute the side chain of the [A] resin only by the specific cyclic structure, or the bivalent chain may be formed on the main chain of the [A] resin. [A] The side chain of the resin may be constituted as a group having a specific cyclic structure.

  The divalent organic linking group is preferably one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group. As said alkylene group, a C1-C20 alkylene group is preferable, More preferably, 1-10 are preferable. Specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, octadecylene, and the like, which may have a branched / cyclic structure or a functional group, and more preferably a methylene group. , Ethylene group and octylene group are preferable. As the arylene group, an arylene group having a total carbon number of 6 to 20 is preferable, and 6 to 12 is more preferable. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched or functional group, and more preferably a phenylene group or a biphenylene group.

  The form in which the specific cyclic structure is bonded to the main chain of the resin [A] via at least an ester group (—COO—) is preferable from the viewpoint of curability during exposure. This form is not limited to the form in which the specific cyclic structure is bonded to the main chain of the resin [A] only through the ester group (—COO—), and the specific cyclic structure contains an ester group (—COO—). The form couple | bonded with the principal chain of [A] resin through the coupling | bonding group of a valence may be sufficient. That is, other atoms and other linking groups may be included between the specific cyclic structure and the ester group and / or between the ester group and the main chain of the [A] resin.

Examples of the linking moiety containing C═O include a moiety represented by the following formula.
In the present specification, the bond is indicated by *.

  Examples of the linking moiety containing P═O include a moiety represented by the following formula.

  Further, specific examples of the 5-membered or 6-membered cyclic structure having a linking site containing C═O and / or a linking site containing P═O are not particularly limited. For example, a structure represented by the following formula Can be mentioned.

  [A] Examples of monomers for introducing a specific cyclic structure into the side chain of the resin include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, ) Acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  [A] Specific monomers for introducing the specific cyclic structure into the side chain of the resin include the following compounds (Compound M-1 to Compound M-16). However, the present invention is not limited to these.

[A] As a monomer for introducing a specific cyclic structure into the side chain of the resin, an appropriately synthesized monomer may be used, or a commercially available product may be used.
This monomer can be synthesized by, for example, the method described in p3871 of macromolecules, Vol36, No. 11, 2003.

  Examples of the commercially available product include 1-AdA from Obata Sangyo Co., Ltd. as Compound M-3, and GBLMA from Obata Sangyo Co., Ltd. as Compound M-10.

~~ Acid group ~~
[A] The resin contains at least one acidic group in the side chain linked to the main chain. A plurality of acidic groups may be contained in the side chain. Moreover, the acidic group may be contained in the side chain of the [A] resin together with the specific cyclic structure and the ethylenically unsaturated bond.
The acidic group may be directly bonded to the main chain of the [A] resin to constitute the side chain of the [A] resin only with the acidic group, or the divalent organic linkage to the main chain of the [A] resin. The side chain of [A] resin may be comprised as a group which couple | bonds through group and has an acidic group. Here, examples of the divalent organic linking group include the divalent organic linking groups exemplified in the description of the specific cyclic structure, and preferred ranges thereof are also the same.

  There is no restriction | limiting in particular as said acidic group, It can select suitably from well-known things, For example, a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group etc. are mentioned. Among these, a carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

  Specific examples of the monomer for introducing the acidic group into the [A] resin can be appropriately selected from known ones, such as (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid. Acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxyl -Polycaprolactone mono (meth) acrylate and the like. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

  Commercially available monomers include Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin-Nakamura Chemical Co., Ltd .: NK Ester CB -1, NK ester CBX-1, manufactured by Kyoeisha Oil and Chemical Co., Ltd .: HOA-MP, HOA-MS, manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100, and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

~~ ethylenically unsaturated bond ~~
[A] The resin contains at least one ethylenically unsaturated bond in the side chain linked to the main chain. [A] In the resin, the ethylenically unsaturated bond is preferably arranged between the main chain via an ester group.
A plurality of ethylenically unsaturated bonds may be contained in the side chain. Moreover, the ethylenically unsaturated bond may be contained in the side chain of the [A] resin together with the specific cyclic structure and / or the acidic group.

  The ethylenically unsaturated bond is bonded to the main chain of the [A] resin via at least one ester group (—COO—), and only the ethylenically unsaturated bond and the ester group [A] resin. The side chain may be constituted. Further, [A] a divalent organic linking group may be further provided between the main chain of the resin and the ester group and / or between the ester group and the ethylenically unsaturated bond. The saturated bond may constitute the side chain of the resin [A] as “a group having an ethylenically unsaturated bond arranged via an ester group between the main chain” and [A] resin. Here, examples of the divalent organic linking group include the divalent organic linking groups exemplified in the description of the specific cyclic structure, and the preferred range is also the same.

The ethylenically unsaturated bond is preferably arranged by introducing a (meth) acryloyl group.
[A] The method of introducing a (meth) acryloyl group into the side chain of the resin can be appropriately selected from known methods. For example, a (meth) acrylate having an epoxy group in a repeating unit having an acidic group is used. Examples thereof include a method of adding, a method of adding a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and a method of adding a (meth) acrylate having a hydroxy group to a repeating unit having an isocyanate group.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

  Although there is no restriction | limiting in particular as (meth) acrylate which has the said epoxy group, For example, the compound represented by following Structural formula (1) and the compound represented by following Structural formula (2) are preferable.

However, in the structural formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

However, in said structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Of the compound represented by the structural formula (1) and the compound represented by the structural formula (2), the compound represented by the structural formula (1) is more preferable than the structural formula (2). In the structural formulas (1) and (2), it is more preferable that L ¹ and L ² are each independently an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) or a structural formula (2), For example, the following exemplary compounds (1)-(10) are mentioned.

~~ Branched and / or alicyclic structure ~~
[A] The resin may contain at least one of a branched and / or alicyclic structure in the side chain bonded to the main chain of the resin. When the photosensitive resin composition contains a branched and / or alicyclic structure [A] resin, when the pattern structure is formed using the photosensitive resin composition, the external force of the pattern structure is increased. It is possible to further enhance the compression elastic modulus when received and the elastic recovery from compression deformation.

[A] When the resin includes a branched and / or alicyclic structure, a plurality of branched and / or alicyclic structures may be included in the side chain of the [A] resin. In addition, when the [A] resin contains a branched and / or alicyclic structure, the branched and / or alicyclic structure is a specific cyclic structure, acidic group, and / or ethylenic group in the side chain of the [A] resin. It may be included together with an unsaturated bond.
In addition, when the [A] resin contains a branched and / or alicyclic structure, the branched and / or alicyclic structure is directly bonded to the main chain of the [A] resin and only the branched and / or alicyclic structure [A It may constitute a side chain of the resin, or [A] a group having a branched and / or alicyclic structure bonded to the main chain of the resin via a divalent organic linking group. You may comprise the side chain. Here, examples of the divalent organic linking group include the divalent organic linking groups exemplified in the description of the specific cyclic structure, and the preferred ranges are also the same.

  The form in which the branched and / or alicyclic structure is bonded to the main chain of the resin [A] via at least an ester group (—COO—) is preferable from the viewpoint of developability and elastic recovery. This form is not limited to the form in which the branched and / or alicyclic structure is bonded to the main chain of the resin [A] only through the ester group (—COO—), and the branched and / or alicyclic structure is an ester group. The form couple | bonded with the principal chain of [A] resin may be sufficient through the bivalent coupling group containing (-COO-). That is, other atoms and other linking groups may be included between the branched and / or alicyclic structure and the ester group, and / or between the ester group and the main chain of the [A] resin. .

  Examples of the branched structure include branched alkyl groups having 3 to 12 carbon atoms, such as i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, and neopentyl group. 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like are preferable. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are more preferable, and i-propyl group, s-butyl group, t-butyl group and the like are particularly preferable.

  Examples of the alicyclic structure include alicyclic hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, A tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like, and groups having these are preferable. Among these, dicyclopentenyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group and the like are more preferable, dicyclopentenyl group, cyclohexyl group, norbornyl Group, isobornyl group, tricyclopentenyl group and the like are more preferable, and dicyclopentenyl group and tricyclopentenyl group are particularly preferable.

  Furthermore, the form comprised by having group represented by following General formula (3) as group which has a branched and / or alicyclic structure is preferable.

  In the general formula (3), X represents a divalent organic linking group, which may be unsubstituted or may have a substituent. y represents 1 or 2, and n represents an integer of 0 to 15.

The divalent organic linking group is preferably one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group, and these may have a substituent.
As said alkylene group, a C1-C20 alkylene group is preferable, More preferably, it is a 1-10 alkylene group. Specific examples include groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, and octadecylene, which may have a branched / cyclic structure or a functional group, and more preferably, A methylene group, an ethylene group and an octylene group;
The arylene group is preferably an arylene group having a total carbon number of 6 to 20, more preferably 6 to 12. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched or functional group, and more preferably a phenylene group or a biphenylene group.
Examples of the substituent when substituted include an alkyl group, a hydroxy group, an amino group, a halogen group, an aromatic ring group, and a group having an alicyclic structure.

  [A] Monomers for introducing a branched and / or alicyclic structure into the side chain of the resin include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides and the like. (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  [A] Specific monomers for introducing a branched structure into the side chain of the resin include i-propyl (meth) acrylate, i-butyl (meth) acrylate, and s-butyl (meth) acrylate. , T-butyl (meth) acrylate, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, (meta ) 3-octyl acrylate, t-octyl (meth) acrylate, etc. Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, etc. are preferable, methacryl More preferred are i-propyl acid and t-butyl methacrylate.

[A] Examples of the monomer for introducing an alicyclic structure into the side chain of the resin include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid 1-adamantyl, (meth) acrylic acid 2-adamantyl, (meth) acrylic acid 3 -Methyl-1-adamantyl, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, ( 3,5,8-triethyl-1-adamantyl (meth) acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, (meth ) 2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7 (meth) acrylate Mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylic acid 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, ( (Meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid fuentyl, (meth) acrylic acid 2,2,5-trimethylcyclohexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid di Examples include cyclopentenyl and tricyclopentenyl (meth) acrylate.
Among these (meth) acrylic acid esters, bulky functional groups improve compression elastic modulus and elastic recoverability, so that (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic Isobornyl acid, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fuentyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylic Dicyclopentenyl acid, tricyclopentenyl (meth) acrylate and the like are preferable, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, (Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid tricyclope Nthenyl is particularly preferred.

[A] Examples of the monomer for introducing an alicyclic structure into the side chain of the resin include compounds represented by the following general formula (4) or (5). Here, in the general formulas (4) and (5), X represents a divalent organic linking group, and R represents a hydrogen atom or a methyl group. y represents 1 or 2, and n represents 0-15. Among general formulas (4) and (5), y = 1 or 2, n = 0 to 8 is preferable, and y = 1 or 2, n = 0 to 4 (more preferably n = 0 to 2). ). Preferred specific examples of the compound represented by the general formula (4) or (5) include the following compounds D-1 to D-11 and T-1 to T-12.
Especially, the compound represented by following General formula (4) is preferable at the point of the elastic recovery rate by the reactivity of a double bond site | part.

  In the general formulas (4) to (5), the divalent organic linking group represented by X may be unsubstituted or may have a substituent, and X in the general formula (3) It is synonymous with the bivalent organic coupling group represented, and its preferable aspect is also the same.

[A] As a monomer for introducing an alicyclic structure into the side chain of the resin, an appropriately produced monomer or a commercially available product may be used.
As said commercial item, Hitachi Chemical Co., Ltd. product: FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M,
H-TCPD-A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M and the like can be mentioned. Among these, FA-512A (S) and 512M are preferable because they are excellent in developability and excellent in the deformation recovery rate.

~~ other monomers ~~
Other groups may be introduced into the [A] resin in the present invention using other monomers.
The other monomer is not particularly limited, and examples thereof include (meth) acrylic acid ester, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, hydrocarbon alkenyl group and the like. Can be mentioned.

There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.
The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  As content rate of the other monomer in said [A] resin, it is preferable that a composition ratio is 1-40 mass%, and it is more preferable that it is 2-30 mass%.

[A] Specific examples of the resin include compounds represented by the following structures (Exemplary Compounds P-1 to P-40).
In addition, x, y, z, and l in the exemplified compound represent the composition ratio (molar ratio) of each repeating unit, and a form configured in a preferable range described later is preferable. Moreover, the form comprised also in the preferable range mentioned later of the weight average molecular weight of each exemplary compound is suitable.

<Synthesis method>
[A] The resin can be synthesized from a two-stage process including a monomer (co) polymerization reaction process and an ethylenically unsaturated group introduction process.
First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

<Carbon number>
[A] The total number of carbon atoms in the main chain of the resin is preferably 10 or more in terms of elastic modulus (hardness). Especially, as for the total carbon number of a principal chain, 10-30 are more preferable, Most preferably, it is 10-15.

<Molecular weight>
[A] The molecular weight of the resin is preferably 10,000 to 100,000 in terms of weight average molecular weight, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of a resin (preferably a copolymer). Further, it is preferable in that the shape formed by the decrease in melt viscosity is difficult to be crushed, in that it is difficult to cause crosslinking failure, and there is no residue in the spacer shape during development.
The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC will be described in detail in the section of the examples described later.

<Glass transition temperature>
[A] The glass transition temperature (Tg) of the resin is preferably 40 to 180 ° C, more preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

<Acid value>
[A] The preferred range of the acid value of the resin varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, and 50 to 130 mgKOH / g. It is particularly preferred. When the acid value is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

<Tg>
The [A] resin has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000 because a spacer having good developability and mechanical strength can be obtained. Preferably, the Tg is 45 to 140 ° C. (further 50 to 130 ° C.) and the weight average molecular weight is 12,000 to 60,000 (further 15,000 to 45,000). .
Furthermore, the preferable example of said [A] resin has more preferable each combination of the said preferable molecular weight, glass transition temperature (Tg), and an acid value.

The resin [A] in the present invention contains a specific cyclic structure (a 5-membered or 6-membered cyclic structure including a moiety represented by C═O and / or a moiety represented by P═O), an acidic group, and ethylene. When a pattern structure (for example, a photospacer for a color filter) is formed, the copolymer is a terpolymer or higher copolymer having a separate unsaturated bond and a separate repeating unit (copolymerization unit). From the viewpoint of deformation recovery rate, development residue and reticulation.
Specifically, the [A] resin has a repeating unit having a specific cyclic structure: X (x mol%), a repeating unit having an acidic group: Y (y mol%), and an ethylenically unsaturated bond. A copolymer of at least terpolymer having at least repeating unit: Z (z mol%) is preferable. Furthermore, you may have other repeating units: L (1 mol%) as needed.
Such a copolymer includes, for example, a monomer having a specific cyclic structure, a monomer having an acidic group, a monomer having an ethylenically unsaturated bond, and other monomers as necessary. And can be obtained by copolymerization.

The copolymer composition ratio when the [A] resin is a copolymer is determined in consideration of the glass transition temperature and the acid value. Although it cannot be generally stated, the following ranges can be adopted.
[A] The composition ratio (x) of the repeating unit having a specific cyclic structure in the resin is preferably 10 to 70 mol%, more preferably 10 to 65 mol%, and particularly preferably 15 to 60 mol%. When the composition ratio (x) is within the above range, good developability is obtained and the developer resistance of the image area is also good.
[A] The composition ratio (y) of the repeating unit having an acidic group in the resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 10 to 50 mol%. When the composition ratio (y) is within the above range, good curability and developability can be obtained.
[A] The composition ratio (z) of the repeating unit having an “ethylenically unsaturated bond” in the resin is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, and particularly preferably 30 to 60 mol%. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, the sensitivity and curability are good, the liquid storage stability after preparation, and the dry film state after application are maintained for a long time. The stability with time is improved.
Furthermore, as the [A] resin, the composition ratio (x) is 10 to 70 mol% (more preferably 10 to 65 mol%, particularly 15 to 60 mol%), and the composition ratio (y) is 5 to 5 mol%. 70 mol% (more preferably 10 to 60 mol%, especially 10 to 50 mol%), and the composition ratio (z) is 10 to 70 mol% (more preferably 20 to 70 mol%, particularly 30 to 60 mol%). %) Is preferred.

[A] When the resin has a “branched and / or alicyclic structure”, the composition ratio (l) of the “branched and / or alicyclic structure” is preferably 10 to 60 mol%, and 15 to 50 mol%. Is more preferable.
In this case, the [A] resin has a composition ratio (x) of 10 to 70 mol% (more preferably 10 to 65 mol%) and a composition ratio (y) of 5 to 70 mol% (more preferably 10 to 65 mol%). 60 mol%, particularly 10 to 50 mol%), and the composition ratio (z) is 10 to 70 mol% (more preferably 20 to 70 mol%, particularly 30 to 60 mol%). The case where (l) is 10 to 60 mol% (more preferably 10 to 50 mol%, particularly 15 to 50 mol%) is preferable.

As content in the photosensitive resin composition of said [A] resin, 5-70 mass% is preferable with respect to the total solid of a composition, and 10-50 mass% is more preferable.
[A] The resin can be used in combination with other resins described later, but it is preferable that the resin is composed only of the [A] resin.

~ Other resins ~
The resin that can be used in combination with the resin [A] is preferably a compound that exhibits swelling properties with respect to an alkaline aqueous solution, and more preferably a compound that is soluble in an alkaline aqueous solution.
As the resin exhibiting swellability or solubility with respect to an alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. Compound (epoxy acrylate compound), vinyl copolymer having (meth) acryloyl group and acidic group in side chain, epoxy acrylate compound and vinyl copolymer having (meth) acryloyl group and acidic group in side chain And the like, and a maleamic acid copolymer are preferable.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

  When the above [A] resin and another resin are used in combination, the total content (solid content) of the resin that can be used in combination with the [A] resin is based on the total solid content of the photosensitive resin layer. 5 to 70 mass% is preferable, and 10 to 50 mass% is more preferable. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the tackiness of the surface of the photosensitive resin layer can be maintained well. When the content is 70% by mass or less, the exposure sensitivity is good. become.

[B] Polymerizable compound The photosensitive resin composition of the present invention contains at least one polymerizable compound. Under the action of radicals from the photopolymerization initiator described later, a polymerization reaction is caused to form a cured film.

The polymerizable compound can be selected from polymerizable compounds constituting a known composition and used, for example, the components described in paragraph numbers [0010] to [0020] of JP-A-2006-23696. And the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.
As the polymerizable compound, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

  In addition, from the viewpoint of further improving the curability at the time of exposure, the [B] polymerizable compound in the present invention includes a 5-membered structure including a site represented by C═O and / or a site represented by P═O. It preferably contains a polymerizable compound having a 6-membered cyclic structure (that is, a specific cyclic structure) and an ethylenically unsaturated double bond (hereinafter also referred to as “specific polymerizable compound”).

  For a site represented by C═O, a site represented by P═O, a linking site containing C═O and / or a 5-membered or 6-membered cyclic structure having a linking site containing P═O, As described in the description of [A] resin, the preferable range is also the same.

The specific polymerizable compound has an ethylenically unsaturated bond.
In this case, from the viewpoint of polymerization curability, the ethylenically unsaturated double bond is more preferably contained as a part of the (meth) acryloyl group in the specific polymerizable compound.

  Specific examples of the specific polymerizable compound include the compounds (formula M-1 to formula M) described above as “specific monomers for introducing a specific cyclic structure into the side chain of the [A] resin”. A compound represented by −16 or the like).

  The specific polymerizable compound preferably has a plurality of ethylenically unsaturated double bonds. Specific examples of the specific polymerizable compound having a plurality of ethylenically unsaturated double bonds (formulas M-101 to M-112) are shown below.

  In the relationship with the [A] resin, the mass ratio ([B] / [A] ratio) of the [B] polymerizable compound to the [A] resin is preferably 0.5 to 2.0. It is more preferably 6 to 1.8, and particularly preferably 0.7 to 1.5. When the ratio [B] / [A] is within the above range, a pattern structure having good developability and mechanical strength can be obtained.

[C] Photopolymerization initiator The photosensitive resin composition of the present invention contains at least one photopolymerization initiator.
There is no limitation in particular as a photoinitiator in this invention, A well-known photoinitiator can be used. Known photopolymerization initiators include, for example, the start described in paragraphs [0010] to [0020] of JP-A-2006-23696 and paragraphs [0027] to [0053] of JP-A-2006-64921. An agent can be mentioned. As examples of known photopolymerization initiators, aminoacetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds other than those described above are preferable in terms of sensitivity.
Specific examples of the aminoacetophenone compound include IRGACURE (Irg) 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.). Specific examples of the acylphosphine oxide compound include DAROCUR TPO, Irgacure (Irg) 819 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like. Specific examples of the oxime ester compound include IRGACURE (Irg) OXE01, CGI242 and the like (manufactured by Ciba Specialty Chemicals Co., Ltd.). The structures of these initiators are shown below.

  0.5-25 mass% is preferable with respect to the total solid of the photosensitive resin composition, and, as for the total amount in the photosensitive resin composition of a photoinitiator, 1-20 mass% is more preferable.

[D] Fine particles The photosensitive resin composition according to the present invention comprises [A] resin, [B] polymerizable compound, and [C] photopolymerization initiator together with [D] fine particles in terms of mechanical strength. It is preferable to contain 1 type.
The fine particles are not particularly limited and may be appropriately selected according to the purpose. For example, extender pigments described in JP-A-2003-302039 [0035] to [0041] are preferable, and among them, good development is preferable. Colloidal silica is preferable from the viewpoint of obtaining a photospacer having good properties and mechanical strength.

  [D] The average particle size of the fine particles is preferably 5 to 50 nm, and preferably 10 to 40 nm in that a high mechanical strength can be obtained when forming a structure that is susceptible to external force such as a photospacer. Is more preferable, and it is especially preferable that it is 15-30 nm.

  [D] The content in the photosensitive resin composition of fine particles (when forming a photo spacer, the photo spacer (or the photosensitive resin layer constituting the photo spacer), from the viewpoint of obtaining a photo spacer having high mechanical strength, The total solid content (mass) in the photosensitive resin composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and particularly preferably 15 to 30 mass%. preferable.

[E] Others The photosensitive resin composition of the present invention includes the [A] resin, the [B] polymerizable compound, the [C] photopolymerization initiator, and the [D] fine particles contained as necessary. In addition, it may further contain other components such as a photopolymerization initiation aid as required.

  The photosensitive resin composition may use a photopolymerization initiation assistant in combination as another additive component. The photopolymerization initiation assistant can be used in combination with a photopolymerization initiator in order to promote polymerization of a polymerizable compound that has been polymerized by the photopolymerization initiator. As the photopolymerization initiation assistant, it is preferable to use at least one amine compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 Examples include '-bis (ethylmethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone is particularly preferable. Further, a plurality of amine-based and other photopolymerization initiation assistants may be used in combination.
Examples of other photopolymerization initiation assistants other than the above include alkoxyanthracene compounds, thioxanthone compounds, and coumarin compounds. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. It is done. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Moreover, a commercially available thing can also be used as a photoinitiation adjuvant. Examples of commercially available photopolymerization initiation assistants include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.).

  As content in the photosensitive resin composition of a photoinitiator adjuvant, 0.6 mass part or more and 20 mass parts or less are preferable with respect to 1 mass part of said photoinitiator, 1 mass part or more and 15 mass parts. Part or less is more preferable, and 1.5 parts by weight or more and 15 parts by weight or less is particularly preferable.

  Further, as other components, they can be selected from components constituting a known composition and used, for example, paragraph numbers [0010] to [0020] of JP-A-2006-23696 and JP-A-2006-64921. Ingredients listed in paragraphs [0027] to [0053] of the gazette.

<Liquid crystal display device>
The liquid crystal display device of the present invention is a liquid crystal display device provided with the color filter substrate of the present invention. Therefore, it is possible to display a high-quality image in which display unevenness is suppressed.
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 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 is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Applicable. 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 spacer can be manufactured by various methods, but it is preferable to manufacture the spacer by applying or transferring the spacer onto the substrate. The production method by coating is preferable in that the process is simple. A manufacturing method by transfer is preferable in that the spacer height is uniform. As a production method by transfer, the method described in Japanese Patent Application No. 2007-185797 is particularly preferable.
The substrate with a light-shielding film 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) ”.

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 of the present invention can achieve a high contrast when combined with a conventionally known three-wavelength cold-cathode tube, but by using red, green and blue LED light sources (RGB-LED) as backlights. A liquid crystal display device with high luminance and high color purity and good color reproducibility can be provided.

  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]
<< Preparation of color filter substrate >>
<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 by coating>
-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 Coating was performed at a coating speed of 120 mm / second by adjusting the interval between the slit and the glass substrate and the discharge amount so as to be 1.2 μm.

-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, a 1.0% developer (1 part by mass of CDK-1 and 99 parts by mass of pure water) of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials), 25 ), The shower pressure was set to 0.20 MPa, development was performed for 60 seconds, and washed with pure water to obtain a developed black matrix. Here, a cross-sectional photograph was taken with an SEM, and the length of the undercut was measured to be 3.0 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 process-
Next, a post-baking process is performed for 40 minutes in a 220 ° C. clean oven, and a black pixel substrate having a colored pixel formation area of 90 μm × 200 μm, a black matrix thickness of 1.2 μm, and a black matrix line width of about 25 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. Moreover, it was 20 micrometers when the line | wire width of this black matrix was measured using the line | wire width measurement system MIM-L (Mikasa Co., Ltd. product).
Furthermore, this black matrix was measured and evaluated by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm and a holding time of 5 seconds. The applied load and the amount of deformation at that time are summarized in Table 3 below.

<3. Preparation of photosensitive coloring composition>
3-1. Preparation of photosensitive coloring composition coating liquid CR-1 for red (R)-
A red (R) dispersion (R-1) was prepared according to the following formulation.
Pigment Red 254 (average particle size 43 nm by SEM observation)
... 11 parts, Pigment Red 177 (average particle size 58 nm by SEM observation)
・ ・ ・ 4 parts ・ Dispersing resin A-3 below ・ 5 parts ・ Dispersant (trade name: Disperbyk-161, manufactured by Big Chemie)
(30% solution of propylene glycol monomethyl ether acetate) 3 parts alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 75/25 [molar ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether Acetate solution (solid content: 50% by mass) ... 9 parts · Solvent B: Propylene glycol monomethyl ether acetate ... 68 parts

  The above components were stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a red (R) dispersion (R-1). Got.

Using the obtained red (R) dispersion liquid (R-1), a photosensitive coloring composition coating liquid CR-1 for red (R) was prepared according to the following formulation.
-Red (R) dispersion (R-1)-100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries, Ltd.-2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate- 8 parts Polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine ... 1 part -Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ... 1 part-Polymerization initiator: Diethylthioxanthone-0.5 part-Polymerization inhibitor : P-methoxyphenol ・ ・ ・ 0.001 part ・ Fluorosurfactant (trade name: Megafac R30, manufactured by Dainippon Ink & Chemicals, Inc.)
・ ・ ・ 0.01 part ・ Nonionic surfactant (trade name: Tetronic R150, manufactured by ADEKA)
・ ・ ・ 0.2 parts ・ Solvent: Propylene glycol n-butyl ether acetate ・ ・ ・ 30 parts ・ Solvent: Propylene glycol monomethyl ether acetate ・ ・ ・ 100 parts A product coating solution CR-1 was obtained.

-3-2. Preparation of photosensitive coloring composition coating liquid CG-1 for green (G)
A green (G) dispersion (G-1) was prepared according to the following formulation.
Pigment Green 36 (average particle size 47 nm by SEM observation)
・ ・ ・ 11 parts ・ Pigment Yellow 150 (average particle diameter by SEM observation: 39 nm)
... 7 parts Dispersion resin A-3 below 5 parts Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
... 3 parts ・ Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 85/15 [molar ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50 mass%) ) 11 parts ・ Solvent: Propylene glycol monomethyl ether acetate 70 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, and a green (G) dispersion (G-1 )

Using the obtained green (G) dispersion liquid (G-1), a photosensitive coloring composition coating liquid CG-1 for green (G) was prepared according to the following formulation.
-Green (G) dispersion (G-1) ... 100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries) ... 2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate .. 8 parts Polymerizable compound: Tetra (ethoxy acrylate) of pentaerythritol 2 parts Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolantolyazine
... 2 parts-Polymerization initiator: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ... 1 part-Polymerization initiator: Diethylthioxanthone ... 0.5 Part / polymerization inhibitor: p-methoxyphenol 0.001 part / fluorine-based surfactant (trade name: Megafac R08, manufactured by Dainippon Ink & Chemicals, Inc.)
・ ・ ・ 0.02 parts ・ Nonionic surfactant (trade name: Emulgen A-60, manufactured by Kao Corporation) ・ ・ ・ ・ 0.5 parts ・ Solvent: Propylene glycol monomethyl ether acetate 120 parts ・ Solvent: Propylene glycol n-Propyl ether acetate ... 30 parts The above composition was mixed and stirred to obtain a photosensitive coloring composition coating solution CG-1 for green (G).

− 3-3. Preparation of photosensitive coloring composition coating solution CB-1 for blue (B)
A blue (B) dispersion (B-1) was prepared according to the following formulation.
Pigment Blue 15: 6 (average particle diameter 55 nm by SEM observation)
・ ・ ・ 14 parts ・ Pigment Violet 23 (average particle diameter 61 nm in SEM observation)
・ ・ ・ 1 part ・ Dispersion resin A-3 below ・ 5 parts ・ Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
... 3 parts ・ Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)・ ・ ・ 4 parts ・ Solvent: Propylene glycol monomethyl ether acetate 73 parts

  The above components were stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a blue (B) dispersion (B-1 )

Using the obtained blue (B) dispersion liquid (B-1), a blue (B) photosensitive coloring composition coating liquid CB-1 was prepared according to the following formulation.
-Blue (B) dispersion (B-1) ... 100 parts-Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer
(= 80/20 [molar ratio] copolymer, molecular weight 30,000), propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) ... 7 parts Epoxy resin: (trade name Celoxide 2080 Daicel Chemical) (Made by Kogyo Co., Ltd.) ... 2 parts UV curable resin: (trade name Cyclomer P ACA-250 made by Daicel Chemical Industries)
(Acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass) ... 4 parts Polymerizable compound: Dipentaerythritol penta Hexaacrylate ... 12 parts-Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyloxime) ethanone ... 3 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Fluorosurfactant (trade name: Megafac R08, manufactured by Dainippon Ink & Chemicals, Inc.)
... 0.02 part, nonionic surfactant (trade name: Emulgen A-60, manufactured by Kao Corporation) ... 1.0 part, solvent: ethyl 3-ethoxypropionate ... 20 parts, solvent: propylene Glycol monomethyl ether acetate: 150 parts The above components were mixed and stirred to obtain a photosensitive coloring composition coating solution CB-1 for blue (B).

<4. Synthesis of Dispersing Resin A-3>
(1. Synthesis of chain transfer agent A3)
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] (the following compound (33)) 7.83 parts, and having an adsorption site, and a carbon-carbon double bond The following compound (m-6) (4.55 parts) having an aldehyde was dissolved in 28.90 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of the mercaptan compound (chain transfer agent A3) shown below was obtained.

(2. Synthesis of dispersion resin A-3)
A mixed solution of 4.99 parts of a 30% solution of chain transfer agent A3 obtained as described above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether, It heated at 90 degreeC under nitrogen stream. While stirring this mixed solution, 0.139 part of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 5.36 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate 9 40 parts of the mixed solution was added dropwise over 2.5 hours. After the completion of the dropwise addition, the mixture was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.046 parts of dimethyl 2,2′-azobisisobutyrate and 4.00 parts of propylene glycol monomethyl ether acetate was added, and further 2 hours. Reacted. To the reaction solution, 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate are added, and cooled to room temperature, whereby a solution (specific dispersion) of the specific dispersion resin A-3 (polystyrene equivalent weight average molecular weight 24000) is obtained. Resin 30% by mass, propylene glycol monomethyl ether 21% by mass, propylene glycol monomethyl ether acetate 49% by mass).
The acid value of the specific dispersion resin A-3 was 48 mg / g. The structure of dispersion resin A-3 is shown below.

<Formation of colored pixels by coating>
-Photosensitive coloring composition layer formation process-
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 gap between the slit and the black matrix substrate so that the layer thickness of the photosensitive coloring composition layer after post-baking is about 2.1 μm, Coating was performed at a coating speed of 120 mm / sec by adjusting the discharge amount.

-Colored layer pre-baking step, colored layer exposure step-
Next, after heating (prebaking treatment) at 100 ° C. for 120 seconds using a hot plate, exposure was performed at 90 mJ / cm ² using a mirror projection type exposure machine (model number MPA-8000, manufactured by Canon Inc.). .
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 process-
Thereafter, a 1.0% developer (1 part by mass of CDK-1 and 99 parts by mass of pure water) of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials), 25 )), The shower pressure was set to 0.2 MPa, 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.

  Subsequently, in the said photosensitive coloring composition layer formation process, colored layer prebaking process, colored layer exposure process, colored layer development process, and colored layer baking process, the photosensitive coloring composition coating liquid CR-1 for red (R) is used. A green pixel was formed in the same manner except that the photosensitive coloring composition coating solution CG-1 for green (G) was used. Thereafter, a blue pixel was formed in the same manner except that the photosensitive coloring composition coating liquid CR-1 for red (R) was replaced with the photosensitive coloring composition coating liquid CB-1 for blue (B).

<Formation of photo spacer>
First, an ITO (Indium Tin Oxide) transparent electrode was further formed on the R pixel, G pixel, B pixel and black matrix of the substrate obtained above by sputtering.

-Film formation process-
Next, on the ITO transparent electrode of the substrate on which the ITO transparent electrode produced as described above was formed by sputtering, a photosensitive resin layer coating solution having the formulation 1 shown in Table 2 below was slit-coated with a spinner. Subsequently, after part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating film, it was pre-baked on a 90 ° C. hot plate for 3 minutes to obtain a film thickness of 5 A photosensitive resin layer having a thickness of 2 μm was formed (film formation step).

-Synthesis of Compound P-1-
7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by Nippon Emulsifier Co., Ltd.) is added in advance to the reaction vessel, the temperature is raised to 90 ° C., and a specific cyclic structure is introduced into the side chain of the resin. 1.28 parts of the compound M-1 (x) as a monomer, 11.7 parts of methacrylic acid (MAA; y), an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) A mixed solution consisting of 08 parts and 55.2 parts of 1-methoxy-2-propanol was dropped into a 90 ° C. reaction vessel over 2 hours under a nitrogen gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, 0.15 part of hydroquinone monomethyl ether and 0.34 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 26.4 parts of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for 2 hours. (GLM-MAA; z). After dripping, after reacting at 90 ° C. for 4 hours while blowing air, a solvent 1-methoxy-2-propyl acetate (MMPGAc, manufactured by Daicel Chemical Industries, Ltd.) is added so that the solid concentration is 45%. Resin solution of the exemplified compound P-1 ([A] resin) (solid content acid value: 76.0 mg KOH / g, Mw; 28,000, 1-methoxy-2-propanol / 1-methoxy-2 -Propyl acetate 45% solution) was obtained (x: y: z = 41 mol%: 24 mol%: 35 mol%).
Here, GLM-MAA shows what glycidyl methacrylate couple | bonded with methacrylic acid. In addition, molecular weight Mw of exemplary compound P-1 showed a weight average molecular weight, and the measurement of the weight average molecular weight was performed using the gel permeation chromatograph method (GPC method). 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".

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, a mask (quartz exposure mask having a circular pattern with a diameter of 15 μm), the mask and the photosensitive resin layer In a state where the color filter substrate placed so as to face each other is set up substantially in parallel and vertically, the distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm, and an intensity of 250 W at 365 nm is passed through the mask. / M ² was irradiated with ultraviolet rays that passed through an ultraviolet transmission filter (UV-35, manufactured by Toshiba Glass Co., Ltd.) (exposure step, exposure amount 200 mJ / cm ² ).

  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 (development process). Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) diluted 10 times with pure water Sprayed with a shower at 33 ° C. for 20 seconds at a cone-type nozzle pressure of 0.02 MPa, the residue around the formed pattern image is removed, and a cylindrical spacer pattern has a spacer spacing of 300 μm × 300 μm. It formed so that it might become.

Next, the substrate provided with the spacer pattern was baked at 130 ° C. for 60 minutes (baking step) to produce a photospacer on the substrate.
Here, about 1000 photo spacers obtained, using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022), an ITO transparent electrode upper surface (of two surfaces parallel to the substrate, from the substrate) The distance from the far side) to the highest position of the photo spacer (hereinafter, this distance is also referred to as “the height of the photo spacer”) was measured, and the average value was taken as the average height of the photo spacer. Moreover, the measurement of the equivalent circle diameter of the obtained photospacer was performed using an SEM photograph. The place where the distance between two arbitrary points on the outer periphery of the photo spacer was the largest from the overhead view shape of the obtained photo spacer was defined as the equivalent circle diameter.
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 an equivalent circle diameter of 15.1 μm and an average height of 4.7 μm. Further, the deformation amount under load was measured in the same manner as the black matrix. The applied load and the amount of deformation at that time are summarized in Table 3 below.

  A color filter substrate was produced as described above.

<< Production of Liquid Crystal Display >>
Separately, a glass substrate was prepared as a counter substrate, and the PVA mode was patterned on the transparent electrode and the counter substrate of the color filter substrate obtained above, and an alignment film made of polyimide was further provided thereon.

-Formation of liquid crystal alignment split projections-
A projection photosensitive resin layer coating solution having the following formulation A was applied onto the ITO transparent electrode on the color filter substrate by a slit coater similar to the above, and dried to form a projection photosensitive resin layer.

<Coating liquid for photosensitive resin layer for protrusions: Formulation A>
・ Positive resist solution (FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.) ・ ・ ・ 53.3 parts ・ Methyl ethyl ketone ・ ・ ・ 46.7 parts ・ The following surfactant 1 ・ ・ ・ 0.04 parts

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

Next, a protective layer having a dry film thickness of 1.6 μm was provided on the photosensitive resin layer for protrusions using an intermediate layer coating liquid having the following formulation P1.
<Intermediate layer coating solution: prescription P1>
PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550)... 32.2 parts Parts ・ Distilled water ・ ・ ・ 524 parts ・ Methanol ・ ・ ・ 429 parts

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. As a result, protrusions patterned in a desired shape were formed on portions above the ITO transparent electrodes of the color filter substrate and above the R, G, and B pixels. 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 3 below.
<Evaluation criteria>
A: There is no unevenness and the display feels very vivid and powerful.
○: 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.

[Example 2]
A liquid crystal display device was prepared in the same manner as in Example 1 except that the baking conditions for the black matrix were set to 240 ° C. for 50 minutes and the baking conditions for the photo spacer were set to 120 ° C. for 40 minutes. The amount of deformation with respect to the load of the black matrix and the photo spacer was as shown in Table 3 below. Table 3 shows the image quality evaluation results.

[Example 3]: Transfer method In Example 2, instead of applying the photosensitive resin layer coating solution (formulation 1), transfer using a photosensitive transfer film for spacers shown below was performed, whereby a photosensitive resin was obtained. A photospacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the layer was formed. The amount of deformation of the black matrix and photospacer obtained at this time with respect to the load was as shown in Table 3. In addition, the obtained photo spacer was cylindrical. The obtained photospacer and liquid crystal display device were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

<Preparation of photosensitive transfer film for spacer>
On a polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm, a thermoplastic resin layer coating solution having the following formulation A is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 15.0 μm. did.

~ Prescription A of coating solution for thermoplastic resin layer ~
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000)
-Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
39.0 parts ・ Surfactant 1 shown below 10.0 parts methanol 90.0 parts 1-methoxy-2-propanol 51.0 parts methyl ethyl ketone 700 parts

* Surfactant 1
・ The following structure 1… 30%
・ Methyl ethyl ketone 70%

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

~ Prescription B of coating solution for intermediate layer ~
Polyvinyl alcohol: 3.22 parts (PVA-205 (saponification rate 80%), manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone: 1.49 parts (PVP K-30, manufactured by ISP Japan Co., Ltd.)
-Methanol ... 42.3 parts distilled water ... 524 parts

  Next, a photosensitive resin layer coating solution having the formulation shown in Table 2 was further applied and dried on the formed intermediate layer, and a photosensitive resin layer having a dry layer thickness of 5.0 μm was laminated.

  As described above, after forming a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (total thickness of three layers: 21.5 μm), the surface of the photosensitive resin layer is formed. Further, a polypropylene film having a thickness of 12 μm was applied as a cover film by heating and pressing to obtain a photosensitive transfer film for spacers.

<Production of photo spacer>
The cover film of the obtained photosensitive transfer film for spacer was peeled off, and the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced in the same manner as in Example 1 was formed by sputtering on the exposed surface of the photosensitive resin layer. The laminate was laminated on top and laminated using a laminator type Lamic II [manufactured by Hitachi Industries, Ltd.] under a linear pressure of 100 N / cm and a pressurization / heating condition of 130 ° C. at a conveyance speed of 2 m / min. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (film formation step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) 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. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 100 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed from the side at an exposure amount of 150 mJ / cm ² (exposure process).

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The mixture was diluted with a ratio at a flat nozzle pressure of 0.04 MPa for 30 seconds at 30 ° C. to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate. Subsequently, a sodium carbonate 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 (development process).
Next, a solution obtained by diluting a detergent (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.)) 10 times with pure water Used, sprayed with a shower at a cone nozzle pressure of 0.02 MPa for 20 seconds at 33 ° C. to remove residues around the formed pattern image, and to form a cylindrical spacer pattern with a spacer spacing of 300 μm × 300 μm. It formed so that it might become.
Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 120 ° C. for 40 minutes (coating heating step) to produce a photo spacer on the color filter substrate. The obtained photospacer had a cylindrical shape with a circle-equivalent diameter of 15.1 μm and an average height of 4.7 μm.

[Comparative Example 1]
In Example 1, a liquid crystal display device was prepared in the same procedure except that the baking at the time of forming the black matrix was changed to 180 ° C. for 30 minutes and the baking at the time of forming the photo spacer was changed to 150 ° C. for 60 minutes. The amount of deformation of the black matrix and photospacer obtained at this time with respect to the load was as shown in Table 3.

From the above results, in this embodiment, the load deformation amount Kb of the black matrix is smaller than the load deformation amount Kp of the photo spacer, the line width of the black matrix is made thinner in order to achieve a higher aperture ratio than in the comparative example. However, it can be seen that the image quality evaluation (display unevenness) is reduced.
Also, in the present embodiment, in the second and third embodiments that satisfy the relationship of the expressions (1) and (2), the image quality evaluation (display unevenness) is reduced compared to the first embodiment, compared to the first embodiment. I understand.

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 fragmentary sectional view of the color filter in which the overlap part was formed. It is a fragmentary sectional view of the color filter which has a horn in an overlap part.

Explanation of symbols

2 Substrate 4 Black matrix (photosensitive dark color composition layer)
6 Coloring pattern (photosensitive coloring composition layer)
8 Overlap part

Claims (5)

In a color filter substrate having a black matrix and a photo spacer,
A color filter substrate satisfying a relationship of Kb ≦ Kp, where Kb (μm) is a deformation amount against load of the black matrix and Kp (μm) is a deformation amount against load of the photo spacer. The color filter substrate according to claim 1, wherein the relationship of the following formulas (1) and (2) is satisfied.
Formula (1): y ₁ ≦ Kb ≦ y ₂ (where y ₁ = 0.001x + 0.05, y ₂ = 0.001x + 0.15),
Formula (2): y ₃ ≦ Kp ≦ y ₄ (where y ₃ = 0.006x + 0.15, y ₄ = 0.006x + 0.25)
(Formula (1) and (2) in, x is the applied load; indicates _mN, y 1 ~y ₄ is the deformation versus load; [mu] m shown.)   The color filter substrate according to claim 1, wherein the black matrix has a line width of 30 μm or less.   4. The color filter substrate according to claim 1, wherein an equivalent circle diameter of the photo spacer is 25 μm or less. 5.   A liquid crystal display device comprising the color filter substrate according to claim 1.