KR20090082114A - Color filter and method of producing thereof, and liquid crystal display device - Google Patents

Abstract

A color filter, a manufacturing method thereof and a liquid crystal display unit employing the same are provided to inhibit the generation of the upthrust portion of the boundary of a black matrix and a coloring pixel in order to secure high quality of images. A method for manufacturing a color filter comprises a black matrix forming step and a coloring pattern forming step. In the black matrix forming step, a photosensitive dark-colored composition layer is formed on a substrate(2); the formed photosensitive dark-colored composition layer is exposed and developed; and a black matrix pattern is formed and baked. In the coloring pattern forming step, a photosensitive coloring composition layer is formed on the substrate on which the black matrix is formed; the formed photosensitive coloring composition layer is exposed and developed; and the developed photosensitive coloring composition layer is baked to form a coloring pattern.

Description

COLOR FILTER AND METHOD OF PRODUCING THEREOF, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a color filter, a manufacturing method thereof, and a liquid crystal display device.

The color filter is an essential component of a liquid crystal display (LCD) or a solid state image pickup device.

For example, liquid crystal displays are used for televisions, and color filters for liquid crystal displays are required to have higher image quality compared with color filters for laptop computers or monitors. In addition, in order to produce large-sized TVs, the size of the substrate has been expanded, and the demand for improvement in yield and cost reduction is increasing.

Regarding the improvement of the image quality, there is a problem that the deterioration of image quality is caused by the fact that the color pattern is raised at the boundary between the black matrix and the color pixel at the time of manufacturing the color filter and the color filter is not flat. See, for example, Japanese Patent Laid-Open No. 9-113721. The elevation of the boundary portion may cause a decrease in contrast or color unevenness.

For this reason, conventionally, it responded by grind | polishing the surface of a color filter after pixel formation, or forming the overcoat layer (henceforth a "OC layer" hereafter) on a pixel. However, the polishing and the formation of the OC layer increase the manufacturing process of the color filter and increase the cost. Moreover, in the case of grinding | polishing, the badness, such as a damage of a color filter, may generate | occur | produce, and the method of being able to skip the grinding | polishing process and / or the formation process of an OC layer was calculated | required.

In contrast, attempts have been made to solve the problem of ridges in the boundary portions by reducing the taper angle of the black matrix (for example, Japanese Patent Laid-Open No. 9-113721 and Japanese Patent Laid-Open No. 2003-161826). See the publication).

Japanese Unexamined Patent Publication No. 2003-161826 also provides a coloring composition only in the black matrix frame by the inkjet method.

However, in the method described in Japanese Patent Laid-Open No. 9-113721, many steps are required to obtain a black matrix having the taper angle. Specifically, after applying and drying the photosensitive deepening composition for black matrix formation on a board | substrate, it was also required to apply a positive resist and to adjust the developing speed ratio of the said photosensitive deepening composition and a positive resist. Moreover, only the adjustment of the taper angle had insufficient effect of suppressing the elevation of the colored pattern. In addition, this technique did not correspond to the large board | substrate of 1m * 1m or more.

On the other hand, in Japanese Patent Laid-Open No. 2003-161826, since a coloring composition is applied to a substrate by an inkjet method to form a coloring pattern, black generated when a coloring pattern is formed by application and / or transfer of the coloring composition. It is not suitable in order to suppress the rise of the coloring pattern in the overlapped part where the matrix and the coloring pattern overlap. Rather, the black matrix is higher than the colored pixel at the boundary between the black matrix and the colored pixel, whereby a step occurs, and the color filter is not smoothed, which may cause a problem of similar quality degradation.

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a high quality image by suppressing the swelling of the colored pattern at the boundary between the black matrix and the colored pixel in a low cost and simple manner without adding a process such as polishing or overcoat layer installation. It is to provide a color filter and a manufacturing method, and a liquid crystal display device that can be obtained.

<1> As a manufacturing method of a color filter,

Forming the photosensitive deep color composition layer on the substrate using the photosensitive deep color composition, exposing the photosensitive deep color composition layer, and developing the photosensitive deep color composition layer after exposure, thereby forming the substrate from an upper end in the photosensitive deep color composition layer. Forming a black matrix pattern in which the distance in the width direction of the black matrix between the line extending in the normal direction and the lower end in the photosensitive deepening composition layer is located at -3.0 to +3.0 µm, A black matrix forming process comprising baking,

The photosensitive coloring composition layer is formed using the photosensitive coloring composition on the said board | substrate with which the black matrix after baking is formed, the said photosensitive coloring composition layer is exposed, the said photosensitive coloring composition layer after exposure is developed, and the developed said photosensitive The coloring pattern formation process is formed by baking a coloring composition layer, and here it forms so that the length in the black-matrix width direction of the overlap part which the said coloring pattern after baking and the said black matrix overlap may be 1.0 micrometer-12 micrometers. Method for producing a color filter having a.

<2> The manufacturing method of the color filter as described in <1> whose thickness of the said photosensitive deepening composition formed on the said board | substrate is 0.2 micrometer-2.2 micrometers.

The manufacturing method of the color filter as described in <1> whose developing temperature is 20 degreeC-35 degreeC, and developing time is 20 second-120 second in the said image development in the <3> said black-matrix formation process.

The manufacturing method of the color filter as described in <3> whose <4> above-mentioned developing temperature is 20 degreeC-30 degreeC, and the said developing time is 30 second-70 second.

<5> The method for producing a color filter according to <1>, wherein the black matrix forming step is after the photosensitive deep color composition layer forming step and further includes a prebaking step before the exposure step.

<6> The manufacturing method of the color filter as described in <5> whose prebaking temperature in the said prebaking process is 65 degreeC-120 degreeC.

<7> The manufacturing method of the color filter as described in <5> whose prebaking time in the said prebaking process is 50 second-300 second.

<8> Exposure is performed through the mask pattern in the said exposure in the said coloring pattern formation process, and the length in the width direction of the black matrix of the overlapping part of an exposure pattern and a black matrix is 3.0 micrometers-8.0 micrometers < The manufacturing method of the color filter of 1>.

The manufacturing method of the color filter as described in <8> whose developing temperature is 20 degreeC-35 degreeC, and developing time is 20 second-120 second in the said image development in the <9> said coloring pattern formation process.

In the said coloring pattern formation process, the said length in the width direction of the black matrix of the overlapping part of an exposure pattern and a black matrix is 2.0 micrometers-10 micrometers, The said developing temperature is 20 degreeC-35 degreeC, The said image development The manufacturing method of the color filter as described in <8> whose time is 20 second-120 second.

The manufacturing method of the color filter as described in <10> whose <11> above-mentioned length is 3.0 micrometers-8.0 micrometers, the said developing temperature is 20 degreeC-30 degreeC, and developing time is 30 second-70 second.

The manufacturing method of the color filter as described in <1> whose distance in the normal direction of a board | substrate between the part which is the furthest from the surface of the <12> overlap part and the parts other than the said overlap part is 0.50 micrometer or less.

The manufacturing method of the color filter as described in <1> whose layer thickness of a <13> photosensitive coloring composition layer is 0.5 micrometer-3.0 micrometers.

<14> The color filter manufactured by the manufacturing method of the color filter in any one of <1>-<13> which has an overlap part which a black matrix and a coloring pattern overlap, and length in the black matrix width direction of the said overlap part. The color filter whose 1.0 micrometer-12 micrometers.

The color filter as described in <14> whose surface in the normal line direction of the board | substrate between the part furthest from the board | substrate surface of the said overlap part and the parts other than the said overlap part among the surfaces of the <15> colored pattern.

<16> A liquid crystal display device provided with the color filter as described in <14>.

<17> A liquid crystal display device provided with the color filter as described in <15>.

[Effects of the Invention]

ADVANTAGE OF THE INVENTION According to this invention, the color filter which can obtain the high quality image by suppressing bulging of the boundary part of a black matrix and a colored pixel by the low cost and the plain method, without adding a process of grinding | polishing or an overcoat layer, etc., and its manufacture A method and a liquid crystal display device can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the color filter of this invention, its manufacturing method, and a liquid crystal display device are demonstrated in detail.

Manufacturing method of color filter

The manufacturing method of the color filter of this invention includes the process of forming a black matrix (black matrix formation process), and the process of forming a coloring pattern (coloring pattern formation process), and may further include another process as needed. .

Hereinafter, the black matrix forming step and the colored pattern forming step will be described.

Black Matrix Forming Process

In the black matrix forming step in the present invention, forming a photosensitive deep color composition layer on the substrate using at least the photosensitive deep color composition (photosensitive deep color composition layer forming step) and exposing the photosensitive deep color composition layer (exposure step). And developing the photosensitive deep color composition layer after the exposure (developmental step) so that the lower end is located at -3.0 to +3.0 µm in the width direction of the black matrix with respect to the upper end in the photosensitive deep color composition layer. A black matrix is formed by forming a black matrix pattern and baking the formed black matrix pattern (baking process). In addition to the above step, other steps may be provided in the black matrix forming step.

Black matrix

In the present invention, the black matrix preferably has an optical density (OD) of 2.0 to 8.0, more preferably 3.0 to 8.0, and more preferably 4.0 to 6.0. When the optical concentration is 2.0 or more, a decrease in display quality of the display device, such as a decrease in contrast can be suppressed.

In addition, the optical density referred to here means ISO Visual (visibility) transmission optical density. As a measuring instrument which can be used for the measurement of ISO Visual transmission optical density, Sakata Ink Engineering Co., Ltd. X-Rite 361T (V) is mentioned, for example.

The black matrix is preferably 5 µm to 30 µm in line width (length in a direction perpendicular to the black matrix longitudinal direction sandwiched between the colored patterns) from the viewpoint of ensuring brightness by high aperture ratio. The thickness of the black matrix (the length in the substrate normal direction of the black matrix) is preferably 0.2 µm to 2.2 µm from the viewpoint of reducing the bulge of the overlapped portion where the black matrix and the coloring pattern overlap (preferably 0.50 µm or less). More preferably, it is 0.2-1.6 micrometers, More preferably, it is 0.5-1.3 micrometers. In this thickness range, the irregularities of the substrate on which the black matrix is formed, that is, the step between the formation region and the non-formation region of the black matrix are appropriate, so that even when a colored pattern (colored pixel) such as RGB is formed thereon after the black matrix is formed, It can be formed with precision.

Photosensitive deep color composition layer forming process

In this process, the photosensitive deep color composition layer is formed on a board | substrate using the photosensitive deep color composition.

Examples of the substrate that can be used in this step include alkali-free glass, soda glass, PYREX® glass, quartz glass and a transparent conductive film attached thereto, and solid-state imaging, for example, for use in liquid crystal display devices and the like. Photoelectric conversion element substrates used for an element etc., for example, a silicon substrate, etc. are mentioned. Also, a plastic substrate can be used. Among them, alkali free glass is preferred from the viewpoint of chemical resistance and heat resistance. On these substrates, a black matrix is first formed in a lattice form or the like so as to isolate each pixel, and then colored pixels are formed in empty portions of the lattice.

Moreover, on these board | substrates, you may form an undercoat layer as needed for the improvement of adhesiveness with an upper layer, prevention of a material diffusion, or planarization of a board | substrate surface. The board | substrate is preferable that a large size (one side about 1 m or more) can achieve the effect of this invention more.

As a method of forming a photosensitive deep color composition layer on a board | substrate, there exists a method of providing a photosensitive deep color composition by application | coating etc., for example on a board | substrate.

As a method of applying the photosensitive deep color composition onto a substrate, various methods such as slit coating, inkjet method, rotation coating, cast coating, roll coating, screen printing, etc. Granting method can be applied. Among them, slit coating is preferable in view of precision and speed. It is preferable to wash | clean a board | substrate with an ultraviolet-ray or various cleaning liquids before these application | coating from a viewpoint of an improvement of applicability | paintability.

Moreover, the method of transferring on the board | substrate the coating film apply | coated and formed by the said provision method on the branch body previously can also be applied.

Regarding the transfer method, paragraphs [0023], [0036] to [0051] of JP 2006-23696A, or paragraphs [0096] to [0108] of JP 2006-47592A are prepared. The method can be suitably used also in the present invention.

The laminator used for the transfer is shown in Fig. WO2006-4225. The large double hinge laminator as described in 24 or the laminator as described in International Application No. JP2007 / 069132 can be suitably used. By using these laminators, high productivity can be obtained.

Although the thickness (for example, application | coating thickness) at the time of providing a photosensitive deepening composition on a board | substrate is suitably adjusted according to the design value of the thickness of the black matrix to form, generally 0.2 micrometer-2.2 micrometers are preferable, and It is more preferable that it is micrometer-1.6 micrometers, and it is most preferable that it is 0.5 micrometer-1.3 micrometers.

Exposure process

In an exposure process, the photosensitive deepening composition layer formed in the said photosensitive deepening composition layer forming process is exposed through a predetermined | prescribed mask pattern, and patterning (only negatively irradiated coating film part is hardened). Especially as radiation which can be used for exposure, ultraviolet rays, such as g line | wire, h line | wire, i line | wire, are used preferably. 5-500 mJ / cm <2> is preferable, 10-300 mJ / cm <2> of an irradiation amount is more preferable, and 10-200 mJ / cm <2> is the most preferable.

The exposure machine may be a proximity type exposure machine, a mirror projection method, or a stepper method.

Developing Process

Subsequently, by performing an alkali developing process, for example, when the photosensitive deepening composition is negative, only the part which photocured by eluting the non-irradiated part in the said exposure in aqueous alkali solution can be left.

As the developing solution, an organic alkali developing solution, an inorganic alkaline developing solution, or a mixture thereof is used.

As an alkali chemicals used for a developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, And organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5.4.0] -7-undecene. The alkaline aqueous solution which diluted these alkaline agents with the pure water so that a density | concentration may be 0.001-10 mass%, Preferably 0.01-1 mass% is used suitably as a developing solution. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes with pure water after image development.

In the present invention, after the present developing step and before the baking step described later, the black matrix pattern is disposed so that the lower end is located at -3.0 to +3.0 µm in the width direction of the black matrix with respect to the upper end in the photosensitive deep color composition layer. To form. The cross-sectional shape of a black matrix pattern, especially the cross-sectional shape of an edge part can be controlled according to each condition of exposure, image development, and the prebaking mentioned later. Therefore, first, the cross-sectional shape of the end portion of the black matrix pattern after the developing step will be described in detail.

In addition, the position of the lower end with respect to the upper end in the said photosensitive deepening composition layer is the width direction of a black matrix between the line extended in the normal direction of a board | substrate from the upper end of the photosensitive deepening composition layer, and the lower end of the photosensitive deepening composition layer. Indicates the distance in. When the photosensitive deepening composition layer after image development is a reverse taper type, the value of the said distance shall be "-".

In the formation process of a black matrix, when developing the photosensitive deepening composition layer after exposure, the surface of a photosensitive deepening composition layer (the surface which does not contact a board | substrate; hereafter is called the same also about a black matrix), and thickness from the said surface ( The layer inside (hereinafter referred to as “upper photosensitive deep color composition layer”) within one third of the photosensitive deep color composition layer in the normal direction of the substrate. Less than one-third is referred to as "advanced black matrix" and progression of the phenomenon and the backside (surface contacting substrate) of the photosensitive deep color composition layer; hereinafter referred to as "backside of black matrix" for the black matrix as well. ), And within two-thirds of the thickness of the photosensitive deepening composition layer from the back surface. When the progress of development of the inside of the layer (hereinafter referred to as "photosensitive deep composition layer lower part". The black matrix is also referred to as "black matrix lower part") is equivalent, the substrate on which the photosensitive deep composition composition layer (black matrix) is formed is black. When cut | disconnected in the width direction of a matrix, the cross-sectional shape of the photosensitive deepening composition layer becomes a substantially vertical shape as shown, for example in FIG. Hereinafter, the cross-sectional shape of the photosensitive deepening composition (black matrix) is made into the cross-sectional shape at the time of cutting | disconnecting in the width direction of a black matrix.

On the other hand, compared with the development of the surface of the photosensitive deepening composition layer and the upper part of the photosensitive deepening composition layer, there may be an excess or shortage in the development of the back surface of the photosensitive deepening composition layer and the bottom of the photosensitive deepening composition. If the development is excessive, the lower portion of the photosensitive deepening composition layer is cut out, and when the substrate on which the photosensitive deepening composition layer (black matrix) is formed is cut in the width direction of the black matrix, the cross-sectional shape of the photosensitive deepening composition layer is, for example, As shown in Fig. 2, the taper has an inverse taper shape. On the other hand, when the development is insufficient, the lower portion of the photosensitive deepening composition layer is protruded, and when the substrate on which the photosensitive deepening composition layer (black matrix) is formed is cut in the width direction of the black matrix, the cross-sectional shape of the photosensitive deepening composition layer is, for example, For example, as shown in FIG. 3, it has a forward taper shape.

In addition, after this developing process and before the baking process mentioned later, when the cross-sectional shape of the photosensitive deepening composition layer is a shape with large reverse taper as shown in FIG. 2, the upper protrusion part is easy to be broken in a developing process, It is easy to produce the defect of planar shape of a black matrix. Therefore, it is preferable that the size of a reverse taper is 3 micrometers or less. That is, it is preferable that a lower end is located at -3.0-0 micrometer with respect to the upper end in the photosensitive deepening composition layer. In addition, when the cross-sectional shape of the photosensitive deep color composition layer is a shape with a large forward taper as shown in FIG. 3, a residue tends to generate | occur | produce in the part which should remove the photosensitive deep color composition layer by lack of image development. Therefore, it is preferable that the size of a forward taper is 3 micrometers or less. That is, it is preferable that the lower end is located at 0-3.0 micrometer with respect to the upper end in the photosensitive deepening composition layer. Therefore, the most preferable shape is a shape in which the end of the photosensitive deep color composition layer as shown in FIG. 1 is substantially perpendicular. After development, it is preferable to have a substantially vertical shape as described above, to heat sagging during subsequent postbaking, and to have an arc-shaped cross-sectional shape.

In reality, there are some variations due to the process unevenness, and if the shape of the photosensitive deepening composition layer after development is a cross-sectional shape where the lower end is located at -3.0 to +3.0 μm in the width direction of the black matrix with respect to the upper end, the problem is a problem. The cross-sectional shape which does not exist and whose lower end is located at -2.0- + 2.0 micrometer with respect to an upper end is preferable.

In order to make the edge part of the said photosensitive deepening composition layer into the vertical cross-sectional shape like FIG. 1 after this developing process and before the baking process mentioned later, it is important to adjust image development conditions suitably. The cross-sectional shape can be adjusted by changing the conditions of image development. Conceptually, as the development is conducted under conditions slightly stronger than those usually used, the reverse taper is produced. On the contrary, as the development is conducted under slightly weak conditions, the taper becomes forward taper.

Stronger conditions are higher temperature, longer time, more flow rate, higher shower pressure, and the like. On the other hand, with weaker conditions, lower temperature, shorter time, less flow volume, lower shower pressure, etc. are mentioned. Especially, adjustment of temperature and time is especially important.

Specifically, 20 to 35 degreeC is preferable and 20 to 30 degreeC of development temperature is preferable from the point which can adjust a cross-sectional shape with high precision. 20 second-120 second are preferable, and, as for image development time, 30 second-70 second are more preferable.

Among these, as a preferable combination of developing temperature and developing time, the combination of 40 second-70 second at the temperature of 23 degreeC, and the combination of 30 second-60 second at the temperature of 25 degreeC is mentioned, for example.

Moreover, since the shower pressure can prevent a black matrix flaw, 0.01 Mpa-0.5 Mpa are preferable, 0.05 Mpa-0.3 Mpa are preferable, and 0.1 Mpa-0.3 Mpa are preferable.

In addition, in order to adjust the cross-sectional shape more finely, it is preferable to add the prebaking process mentioned later to a black matrix formation process.

Baking process

Next, heat processing called baking process (post-baking) is given to a black matrix pattern. Baking is a heat treatment after development for completely curing the photosensitive deep color composition, and usually a thermosetting treatment at 150 ° C to 260 ° C.

As for baking temperature, 150 degreeC-260 degreeC is preferable, 180 degreeC-260 degreeC is more preferable, and 200 degreeC-250 degreeC is the most preferable. 10 minutes-150 minutes are preferable, as for baking time, 20 minutes-120 minutes are more preferable, and 30 minutes-90 minutes are the most preferable.

After the development process, the composition layer near the vertical cross-sectional shape as shown in Fig. 1 whose end portion is close to the vertical cross-sectional shape is baked under the above conditions, whereby the cross-sectional shape can be adjusted to a shape close to an arc as shown in FIG. 4. Before the photosensitive deep color composition is completely cured by heating the photosensitive deep color composition after development by baking treatment, the edge portion is rounded by the surface tension once by the state of low luminance, and then cured, and the above-described shape is formed.

Easiness of rounding of the edges due to heating after this development (hereinafter may be referred to as "heat deflection") also changes depending on the composition of the photosensitive deep color composition, prebaking conditions, exposure conditions, or developing conditions. In general, the lower the concentration of the light-shielding agent in the composition ratio of the photosensitive deepening composition is, the lower the concentration of the light-shielding agent tends to be thermally sag. For example, when the film thickness after baking is 1.4 micrometers, the light-shielding agent density | concentration which becomes OD (optical density of a black matrix) to 4.1 can be used preferably. On the other hand, when the film thickness after baking is 1.0 micrometer, heat sag hardly arises at the light-shielding agent density | concentration which becomes OD of 4.1.

Moreover, as another means of generating heat sag, devising the composition of a monomer is mentioned. For example, as described in Japanese Patent Laid-Open No. 2004-163917, a mixture of a trifunctional or higher monomer and a bifunctional monomer can be preferably used as the monomer.

In addition, the lower the prebaking temperature, the shorter the prebaking time, the more likely to sag the heat, the higher the prebaking temperature and the longer the prebaking time, the less likely to sag the heat; the weaker the exposure intensity, the easier to sag the heat; The weaker the development conditions are, the more prone to heat sag, and the stronger the tendency of heat sag. In addition, the post-baking temperature is slightly lower and the one which is long-term tends to be drooped, and the one whose temperature is high and short-term tends to be difficult to be drooped.

As shown in FIG. 4, when the point where an arc starts from the flat black matrix surface after baking is set to P point, and the horizontal distance with the Q point which shows the horizontal end of a black matrix is made into a taper length, the said taper length is It is preferable that it is 2.0 micrometers-15.0 micrometers, and it is preferable that the said taper length is 2.5 micrometers-10.0 micrometers. In addition, it is preferable that Q point is located in the lower part in the layer which contact | connects a board | substrate, or its vicinity.

FIG. 5 is a cross-sectional view when a colored pixel is formed on a substrate on which a black matrix having a taper length in the above range is formed. In this manner, the ridges of the overlapping portions of the black matrix and the colored pixels can be suppressed.

Baking treatment can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), or a high frequency heater, so that the photosensitive deepening composition layer after image development may be set to said conditions.

Other process

In the black matrix forming step of the present invention, a prebaking step may be further added after the photosensitive deep color composition layer forming step and before the exposure step. Moreover, after the said development process and before the said baking (post baking) process, you may include the process of hardening the formed black matrix by exposure as needed.

Prebaking Process

As mentioned above, in order to adjust the cross-sectional shape after image development of a black matrix, in addition to adjusting the conditions of exposure and / or image development in a black matrix formation process, it is preferable to adjust prebaking conditions suitably. In the black matrix forming step in the present invention, the taper becomes inverse taper when it is performed at a lower temperature than prebaking conditions which are often used, and tends to be a forward taper when it is performed at a high temperature.

Specifically, in the case of prebaking with a hot plate, the prebaking temperature is preferably 65 ° C to 120 ° C. By setting it as 65 degreeC or more, peeling of the photosensitive deepening composition layer can be prevented during a developing process, and by setting it as 120 degrees C or less, it can be set as the state which the image development of the lower part of the photosensitive deepening composition layer advances. More preferably, it is 70 degreeC-100 degreeC, and 75 degreeC-90 degreeC is the most preferable. Moreover, as for a prebaking time, 50 second-300 second are preferable, 90 second-200 second are more preferable, and 100 second-180 second are the most preferable. By prebaking on the said conditions, the cross-sectional shape after image development of the photosensitive deepening composition layer becomes easy to adjust.

In addition, prebaking can also be performed in oven, and also in that case, the cross-sectional shape after image development can be adjusted by setting the prebaking conditions similar to the above suitably.

Coloring pattern forming process

In the coloring pattern forming step of the present invention, forming a photosensitive coloring composition layer on the substrate on which the photosensitive deepening composition layer (black matrix) after baking is formed (photosensitive coloring composition layer forming step), Exposing the photosensitive coloring composition layer (color layer exposure step), developing the photosensitive coloring composition layer after exposure (color layer development step), baking the developed photosensitive coloring composition layer (color layer baking step ), A coloring pattern is formed such that the length in the black matrix width direction of the overlap portion overlapping with the black matrix after the baking becomes 1.0 µm to 12 µm. In a coloring pattern formation process, you may further form another process, such as a prebaking process, in addition to the said process.

First, the "overlap" will be described.

Overlap

When forming a coloring pattern (colored pixel) by apply | coating the photosensitive coloring composition on the board | substrate with a black matrix, the photosensitive coloring composition is made so that the photosensitive coloring composition and a black matrix may overlap so that a clearance gap may not arise between a black matrix and a colored pixel. It is common to form colored pixels by slightly covering (overlapping) the black matrix. In this invention, in addition to the cross-sectional shape after image development of the black matrix mentioned above, a high quality color filter and a liquid crystal display device can be obtained by adjusting the length of an overlap part to 1.0 micrometer-12 micrometers.

The said "length of an overlap part" means the length in the width direction of the black matrix of the overlap part in which the black pattern and the coloring pattern formed using the photosensitive coloring composition layer overlap. This will be described in more detail with reference to the drawings.

FIG. 6 shows that the photosensitive coloring composition layer 6 is formed by applying the photosensitive coloring composition onto the substrate 2 on which the black matrix 4 is formed, and the black matrix 4 and the photosensitive coloring composition layer 6 overlap each other. It is a partial sectional view of the color filter which shows the state in which the part 8 was formed. Here, the overlap part 8 is a region of length b, and the length b of the overlap part 8 opposes the photosensitive coloring composition layer 6 in the width direction of the black matrix 4. The width of the black matrix 4 between the outermost end S on the side and the outermost end T positioned on the black matrix 4 of the photosensitive coloring composition layer 6 formed so as to overlap the black matrix 4. It can obtain | require as distance (length) of a direction.

In fact, in obtaining the length b of the overlap part 8, it can obtain | require by cutting a color filter in the direction perpendicular | vertical to the longitudinal direction of the pattern of the black matrix 4, and measuring it from the cross section.

The length b of the overlap portion 8 is preferably 1.0 µm to 12 µm, more preferably 1.0 µm to 10 µm, from the viewpoint of reducing the elevation of the overlap portion (preferably 0.50 µm or less). 2.0 micrometers-8.0 micrometers are the most preferable.

Moreover, by making the length b of the said overlap part 8 into 12 micrometers or less, a color filter and a display apparatus can be manufactured stably on a large board | substrate (one side length is 1 m or more).

The length b of the overlap 8 can be adjusted by changing the exposure pattern position and image development conditions of the photosensitive coloring composition layer. Specifically, as the amount of overlap with the black matrix of the exposure pattern decreases, the amount of overlap can be reduced. In addition, as the developing conditions are weakened, for example, as the developing temperature is lowered, or as the developing time is shortened, the overlap amount can be increased.

More specifically, in order to make the length b of the said overlap part 8 into 1.0 micrometer-12 micrometers, the distance (length) in the width direction of the black matrix of the overlapping part of an exposure pattern and a black matrix is 3.0 micrometers- It is preferable to set it to 8.0 micrometers. Moreover, it is preferable to make image development temperature 20 degreeC-35 degreeC, and it is more preferable to set it as 20 degreeC-30 degreeC. Moreover, it is preferable to make developing time into 20 second-120 second, and it is more preferable to set it as 30 second-70 second.

As a preferable combination of each of the above conditions, the combination of the exposure pattern and the overlapped portion of the black matrix is 2.0 µm to 10 µm, the developing temperature is 20 ° C to 35 ° C, and the developing time is 20 seconds to 120 seconds. desirable.

A more preferable combination is a combination in which the length of the overlapped portion of the exposure pattern and the black matrix is 3.0 µm to 8.0 µm, the developing temperature is 20 ° C to 30 ° C, and the developing time is 30 seconds to 70 seconds.

As described above, the photosensitive coloring composition is coated on the black matrix so that the black matrix and the photosensitive coloring composition layer partially overlap in the overlap portion of the black matrix and the photosensitive coloring composition layer, so that the powder is raised. By reducing the degree of ridge of this overlap part, the confusion of liquid crystal orientation or light leakage can be suppressed, and a high quality image can be obtained. The elevation of an overlap part is demonstrated using drawing.

7 forms the photosensitive coloring composition layer by apply | coating the photosensitive coloring composition on the board | substrate 2 in which the black matrix 4 was formed, and performing exposure and image development, etc., to form the coloring pattern 6, and the black matrix 4 ) And the colored pattern 6 are partial cross-sectional views of the color filter showing a state in which a ridge is generated in the overlapped portion 8.

The above-mentioned "degree of bump of an overlap part" is more specifically, the surface of the board | substrate 2 in the said overlap part 8 (black matrix 4 of the board | substrate 2 and the coloring pattern of the surface of the coloring pattern 6). Surface in contact with (6)] and the distance in the normal direction of the board | substrate between the flat surface part other than the said overlap part 8 is said. In other words, the "degree of bulge of the overlapped part" refers to the normal direction of the substrate between the surface of the substrate 2 and the part farthest from the surface of the substrate 2 of the overlapped part 8 among the surfaces of the colored pattern 6. The distance e in which the distance d in the normal direction of the substrate between the surface of the substrate 2 and the portions other than the overlap portion 8 among the surfaces of the colored pattern 6 is subtracted from the distance c in the substrate c. Say.

Hereinafter, the distance e is referred to as "height of uplift." The height of the ridge is preferably 0.50 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. By suppressing the height of this elevation as mentioned above, when a color filter is produced and an image is displayed, the confusion of liquid crystal orientation or light leakage can be suppressed, and a high quality image can be obtained.

The height of the ridge can be adjusted by appropriately setting the cross-sectional shape (ie, taper length) after baking of the black matrix, the length of the overlap portion, and the thickness of the black matrix.

The preferred combination of the taper length, the length b of the overlap portion 8, and the thickness of the black matrix has a taper length of 2.0 µm to 15 µm, length of the overlap portion of 1.0 µm to 12 µm, and black It is preferable that the thickness of the matrix is 0.2 µm to 1.5 µm. A more preferable combination is to make taper length 2.5 micrometer-10 micrometers, length b of the overlap part 8 make 2.5 micrometers-8.5 micrometers, and make black matrix thickness 0.5 micrometer-1.3 micrometers.

Next, the various processes performed in the coloring pattern formation process in this invention are demonstrated.

Photosensitive coloring composition layer forming process

In the photosensitive coloring composition layer forming process, the photosensitive coloring composition layer is formed using the photosensitive coloring composition on the board | substrate with which the photosensitive deepening composition layer (black matrix) after baking is formed.

As a method of forming a photosensitive coloring composition layer on a board | substrate with a black matrix, the same method as the method of forming a photosensitive deepening composition layer on a board | substrate, ie, a coating method or a transfer method, can be used.

Especially, the method of apply | coating the photosensitive coloring composition to the board | substrate surface in which the black matrix was formed with the slit coater etc. is preferable at the point which can achieve the effect of this invention well.

The layer thickness of the photosensitive coloring composition layer is preferably 0.5 µm to 3.0 µm, more preferably 1.0 µm to 2.5 µm, in order to obtain a sufficient color reproduction region and to obtain sufficient luminance of the panel.

Colored layer exposure process

In the colored layer exposure step, the photosensitive coloring composition layer is exposed.

The exposure process of the photosensitive coloring composition layer can be performed similarly to the exposure process of the photosensitive deepening composition layer. When forming a multicolored coloring pattern, it exposes for every color through the predetermined | prescribed mask pattern for each color, and patterns the photosensitive coloring composition layer of each color irradiated light (in the case of negative photosensitive coloring composition, the light-irradiated part) Can only cure).

Colored layer developing process

In the colored layer developing step, the photosensitive coloring composition layer after exposure is developed.

The image development processing of the photosensitive coloring composition layer after exposure can perform the operation similar to the operation described in description of the image development process of the photosensitive deepening composition layer, and can use the developing solution demonstrated in the said image development process suitably.

As development conditions, in order to adjust the length of the overlap part and the height of ridge | float which generate | occur | produce in the overlap part of a black matrix and a colored pixel, it is preferable to develop the photosensitive coloring composition layer on the developing conditions described in the description of the said overlap.

Colored layer baking process

In the colored layer baking step, the developed photosensitive coloring composition layer is baked.

As a method of baking the photosensitive coloring composition layer after image development, the method similar to the baking process of baking the photosensitive deepening composition layer mentioned above can be used.

In addition, when forming the coloring pattern of multiple colors, such as three colors of RGB (Red, Green, Blue), the formation, exposure, image development, and baking cycle of the photosensitive coloring composition layer may be repeated by the desired number of colors, and every color After forming, exposing, and developing a photosensitive coloring composition layer, you may bake all the color components at the same time last. Thereby, the color filter provided with the black matrix and the colored pixel which consists of desired color is produced.

Other process

Also in a coloring pattern formation process, in order to dry a photosensitive coloring composition after a photosensitive coloring composition layer forming process and before a colored layer exposure process, you may provide the process (color layer prebaking process) of prebaking a photosensitive coloring composition layer.

60 degreeC-140 degreeC is preferable, and, as for the prebaking temperature of the photosensitive coloring composition layer, 80 degreeC-120 degreeC is more preferable. 30 second-300 second are preferable, and, as for a prebaking time, 80 second-200 second are more preferable.

Next, the photosensitive coloring composition and photosensitive deepening composition used for the manufacturing method of the color filter of this invention are demonstrated in detail.

Photosensitive coloring composition

The photosensitive coloring composition used for coloring pattern formation of the color filter of this invention is a radiation sensitive composition (for example, the radiation sensitive composition hardened | cured by light irradiation in the case of a negative composition), (A-1) It is preferable to contain a coloring agent, (B) binder polymer, (C-1) polymeric compound, (D) photoinitiator, and (E) solvent, and if desired, other additives, such as a polymer dispersing agent or surfactant, You may contain more.

(A-1) Colorant

The colorant may be appropriately selected from dyes and pigments. Although the pigment used as a coloring agent may be an inorganic pigment or an organic pigment, a pigment with a small particle size is preferable as long as it considers that it is preferable that it is a high transmittance. It is preferable that average particle size is 10 nm-100 nm, More preferably, it is the range of 10 nm-50 nm. In the photosensitive coloring composition used in the present invention, pigment dispersibility and dispersion stability are good even when the size of the colorant is small by using the polymer dispersant described later, so that a colored pixel excellent in color purity is formed even if the film thickness is thin. can do.

As an example of the inorganic pigment which can be used as a coloring agent for coloring pattern (color pixel) formation, metal compounds, such as a metal oxide and a metal complex salt, are mentioned. Specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

As the organic pigment, for example,

C.I. Pigment yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C.I. Pigment orange 36, 38, 43, 71;

C.I. Pigment red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment violet 19, 23, 32, 37, 39;

C.I. Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment green 7, 36, 37;

C.I. Pigment brown 25, 28;

C.I. Pigment Black 1

Etc. can be mentioned.

Although it does not specifically limit in this invention, The following pigment is more preferable:

C.I. Pigment yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;

C.I. Pigment orange 36, 71;

C.I. Pigment red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;

C.I. Pigment violet 19, 23, 37;

C.I. Pigment blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37.

These organic pigments may be used alone or in combination in various ways to increase color purity. The specific example of a combination is shown below.

For example, as a pigment for red phase (R), an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a bis azo yellow pigment, an isoindolin yellow pigment, and Mixing with at least one of the quinophthalone yellow pigments and / or the perylene red pigments, and the like can be used. For example, as an anthraquinone pigment, C.I. Pigment Red 177 is mentioned, As a perylene pigment, C.I. Pigment Red 155 or C.I. Pigment red 224. Examples of the diketopyrrolopyrrole pigment include C.I. Pigment red 254, and at least one of them and C.I. Preference is given to mixing Pigment Yellow 139. In addition, the mass ratio (red pigment: yellow pigment) of the red pigment and the yellow pigment is preferably 100: 5 to 100: 50 from the viewpoint of obtaining sufficient color purity and suppressing the deviation from the color of the NTSC (National Television System Committee) standard. Do. Especially as said mass ratio, the range of 100: 10-100: 30 is optimal. In addition, in the case of the combination of red pigments, it can adjust to chromaticity.

As the pigment for the green phase (G), a halogenated phthalocyanine pigment alone or a mixture of this and a bis azo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindolin yellow pigment can be used. . For example, as such an example, C.I. Pigment green 7, 36, or 37, and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Mixing with Pigment Yellow 185 is preferred. As for mass ratio (green pigment: yellow pigment) of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable from a viewpoint of obtaining sufficient color purity and suppressing the deviation from the color of NTSC standard. As mass ratio, the range of 100: 30-100: 120 is especially preferable.

As a pigment for a blue phase (B), a phthalocyanine pigment can be used individually or the mixture of this and a dioxadine purple pigment can be used. For example, C.I. Pigment Blue 15: 6 and C.I. Mixing of pigment violet 23 is preferred. As for mass ratio (blue pigment: purple pigment) of a blue pigment and a purple pigment, 100: 0-100: 50 are preferable, More preferably, it is 100: 5-100: 30.

As for content of the (A-1) coloring agent (pigment) in the photosensitive coloring composition layer used for this invention, 25-75 mass% is preferable with respect to the total solid (mass) of the said composition, and 32-70 mass% is more desirable. (A-1) When content of a coloring agent (pigment) is in the said range, color concentration is sufficient and it is effective in ensuring the outstanding color characteristic.

(B) binder polymer

It is preferable that the said photosensitive coloring composition of this invention contains a binder polymer for the purpose of the improvement of a film | membrane characteristic, a provision of image development characteristic, etc. The following alkali-soluble resin can be used as a binder polymer.

As alkali-soluble resin used by this invention, it is a linear organic high molecular polymer, group which promotes at least 1 alkali solubility in a molecule | numerator (preferably an acryl copolymer or a molecule which has a styrene copolymer as a main chain) (for example, It can select suitably from alkali-soluble resin which has a carboxyl group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group etc.).

As a more preferable example of the said alkali-soluble resin, the polymer which has a carboxylic acid in a side chain, for example, Unexamined-Japanese-Patent No. 59-44615, Unexamined-Japanese-Patent No. 54-34327, Unexamined-Japanese-Patent No. 58-12577 , Methacrylic acid copolymers, acrylic acid copolymers, and itas as described in Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Publication No. 59-71048 A choline acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer, and an acidic cellulose derivative having a carboxylic acid in the side chain, and an acid anhydride added to a polymer having a hydroxyl group, and the like. And acrylic copolymers.

The acid value of the said alkali-soluble resin is 10-200 mgKOH / g, Preferably it is 30-180 mgKOH / g, More preferably, 50-150 mgKOH / g is preferable.

As a specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and another monomer copolymerizable with this is preferable especially. As an example of the other monomer copolymerizable with the said (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include a compound represented by CH ₂ = C (R ¹ ) (COOR ³ ), wherein R ¹ represents a hydrogen atom or C 1 to C 1. An alkyl group of 5 is represented, and R ³ represents an alkyl group of 1 to 8 carbon atoms or an aralkyl group of 6 to 12 carbon atoms. As a specific example, 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 a C1-C8 alkyl group), hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. are mentioned.

Moreover, the resin which has a polyalkylene oxide chain in a molecular side chain is also mentioned as a preferable example of alkali-soluble resin. As said polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or these can be used together, 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 / or a polypropylene oxide chain, 2-12 are more preferable. As an example of the acryl copolymer which has a polyalkylene oxide chain in a side chain, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and poly (ethylene glycol propylene glycol) mono (meth) acrylate, And compounds which alkyl-blocked these terminal OH groups, for example, methoxy polyethylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, and methoxy poly (ethylene glycol propylene glycol) mono ( The acrylic copolymer which uses a meta) acrylate etc. as a copolymerization component is mentioned.

Examples of the vinyl compound include a compound represented by 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. Indicates. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macro monomers, and polymethyl methacrylate macromonomers.

The other monomer which can be copolymerized can be used individually by 1 type or in combination of 2 or more type. Especially among these, the multicomponent copolymer which consists of a benzyl (meth) acrylate / (meth) acrylic acid copolymer, and benzyl (meth) acrylate / (meth) acrylic acid / another monomer is preferable.

As mentioned above, an acrylic resin has an acid value of 20-200 mgKOH / g. If the acid value is 200 or less, the solubility of the acrylic resin in alkali is not too large, and the development proper range (developing latitude) can be prevented from narrowing. On the other hand, when it is 20 or more, since the solubility to alkali is unlikely to become small, prolongation of development time can be prevented.

In addition, the weight average molecular weight (Mw) [polystyrene conversion value measured by GPC method (Gel Permeation Chromatography)] of an acrylic resin is further, in order to implement | achieve the viscosity range which is easy to use in the process of apply | coating a photosensitive coloring composition, and also film strength It is preferable that it is 2,000-100,000, More preferably, it is 3,000-50,000 in order to ensure the

Moreover, in order to improve the crosslinking efficiency of the photosensitive coloring composition in this invention, you may use resin which provided the polymerizable group to alkali-soluble resin individually or in combination with alkali-soluble resin which does not have a polymerizable group. As an example of resin which provided the polymerizable group to alkali-soluble resin, the polymer which contained an aryl group, a (meth) acryl group, or an aryloxyalkyl group etc. in a side chain is mentioned. Alkali-soluble resin which has a polymerizable double bond can be developed by alkaline developing solution, and also has photocurability and thermosetting. Examples of the polymer containing these polymerizable groups are shown below. However, the polymer is not limited as long as it contains an alkali-soluble group such as a COOH group or an OH group and a carbon-carbon unsaturated bond in one molecule.

(1) A urethane-modified polymerization obtained by reacting an isocyanate group with an OH group in advance to leave one unreacted isocyanate group and at least one compound containing at least one (meth) acryloyl group and an acrylic resin containing a carboxyl group. Acrylic double bond-containing acrylic resin,

(2) an unsaturated group-containing acrylic resin obtained by reaction of an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond together in a molecule;

(3) acid pendant 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, resins of (1) and (2) are particularly preferable.

As a specific example, for example, a copolymer of 2-hydroxyethyl acrylate having an OH group with methacrylic acid containing a COOH group and a monomer such as an acrylic compound or a vinyl compound copolymerizable therewith may be used in the OH group. The compound etc. which are obtained by making a compound (for example, glycidyl acrylate compounds etc.) which have an epoxy ring which has reactivity with the unsaturated carbon-to-carbon unsaturated bond group react can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group can be used in addition to the epoxy ring.

Moreover, saturated or unsaturated polybasic acid anhydride is reacted with the compound obtained by making the compound which has the epoxy ring of Unexamined-Japanese-Patent No. 6-102669 and Unexamined-Japanese-Patent No. 6-1938, and the compound obtained by making unsaturated carboxylic acid, such as acrylic acid, react. The reactant obtained by making it available can also be used.

As an example of the compound which also has an alkali solubilizer and a carbon-to-carbon unsaturated group, such as a COOH group, it is the DIANAL NR series (made by Mitsubishi Rayon Corporation); Photomer 6173 (COOH group-containing polyurethane acrylic oligomer, Diamond shamrock Co. Ltd., make); Viscote (VISCOTE) R-264, KS resist 106 [all made by Osaka Yuki Kagaku Kogyo Co., Ltd.]; Cyclomer (CYCLOMER ) P series, Placcel CF200 series (both manufactured by Daicel Kagaku Kogyo Co., Ltd.); Ebecryl 3800 (made by Daicel Cytec Co., Ltd.), etc. are mentioned.

It is preferable that it is the range of 3-30 mass% in the total solid of the photosensitive coloring composition layer, and, as for the addition amount of alkali-soluble resin, 5-20 mass% is more preferable.

At the time of preparation of the photosensitive coloring composition, it is preferable to further add the following epoxy resin to the said alkali-soluble resin as a binder polymer further. As an epoxy resin, the compound which has two or more epoxy rings in a molecule | numerator, such as a bisphenol-A epoxy resin, a cresol novolak-type epoxy resin, a biphenyl type epoxy resin, and an alicyclic epoxy compound, is mentioned.

For example, as an example of bisphenol-A epoxy resin, EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF -8170, YDF-170, etc. (above, manufactured by Tokasei Co., Ltd.), DENACOL EX-1101, EX-1102, EX-1103, etc. [Nagase Chemtex Co., Ltd.], Fraxel GL-61 , GL-62, G101, G102 (above, the Daicel Kagaku Kogyo Co., Ltd. product) etc. are mentioned. In addition, bisphenol F type epoxy resin similar to these and bisphenol S type epoxy resin can also be mentioned as usable.

Moreover, epoxy acrylates, such as Ebecryl 3700, 3701, and 600 (more than a Daicel Cytec Co., Ltd. product), can also be used. As an example of a cresol novolak-type epoxy resin, Epoto YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, Totokasei Co., Ltd. make), Denacol EM-125, etc. [ The above is mentioned by Nagase Kasei. As an example of a biphenyl type epoxy resin, 3,5,3 ', 5'- tetramethyl-4,4'- diglycidyl biphenyl etc. are mentioned. Examples of the alicyclic epoxy compound include CELLOXIDE 2021, 2081, 2083, 2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, and EHPE-3150. Gaku Kogyo Co., Ltd.], Santoto ST-3000, ST-4000, ST-5080, ST-5100, etc. (above, manufactured by Totokasei Co., Ltd.), Epiclon 430, East 673, East 695, East 850S and 4032 (above, the Dainippon Ink & Chemicals Co., Ltd. product) etc. are mentioned. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o- Phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, epoxide YH-434 and YH-434L, which are amine epoxy resins, and glycidyl esters modified with dimer acid in the skeleton of bisphenol A epoxy resins can also be used. Can be.

Among these, preferable resin is "the number of molecular weight / epoxy ring" is 100 or more, More preferably, it is 130-500. If the "molecular weight / number of epoxy rings" is small, the curability is high, the shrinkage during curing is large, and if it is too large, the curability is insufficient, the reliability is poor or the flatness is poor.

Specific examples of the preferred compound include Efototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Fraxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl- 4,4 'diglycidyl biphenyl, ceoxide 2021, 2081, eporide GT-302, GT-403, EHPE-3150, etc. are mentioned.

(C-1) polymerizable compound

It is preferable that the photosensitive coloring composition used for this invention contains the (C-1) polymeric compound.

The polymerizable compound which can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such compound groups are widely known in the industrial field and can be used in the present invention without particular limitation. These can be, for example, chemical forms such as monomers, prepolymers (ie dimers or trimers) and oligomers, or mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its esters, and amides are mentioned. Preferably, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds or amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds are used. Furthermore, addition reaction products of unsaturated carboxylic esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups or mercapto groups with monofunctional or polyfunctional isocyanates or monofunctional or polyfunctional epoxys And dehydration condensation reaction products of the above unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional carboxylic acids are also preferably used. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines or thiols, and also halogen or tosyl jade Substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a period and monofunctional or polyfunctional alcohols, amines or thiols are also preferable. As another example, it is also possible to use a compound group obtained by replacing the above unsaturated carboxylic acid with unsaturated phosphonic acid, styrene, vinyl ether or the like.

Specific examples of ester monomers of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene glycol as acrylic acid esters. Diacrylate, neopentylglycol diacrylate, trimetholpropane triacrylate, trimetholpropane tri (acryloyloxypropyl) ether, trimetholethane triacrylate, hexanediol diacrylate, 1,4 -Cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylic re Sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate, etc. Can;

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimetholpropane trimethacrylate, trimetholethane trimethacrylate, ethylene glycol dimethacrylate Methacrylate, 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-hydroxypropoxy) phenyl] dimethylmethane, and bis- [p- ( Methacryloxyethoxy) phenyl] dimethyl methane, etc .;

As the itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetrayi Taconate, etc .;

Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, and the like;

As isocrotonic acid ester, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. are mentioned;

Examples of the maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

As examples of other esters, for example, the aliphatic alcohol esters described in JP-A-51-47334, JP-A-57-196231, JP-A-59-5240, and JP-A-JP The ester which has the aromatic skeleton of Unexamined-Japanese-Patent No. 59-5241, Unexamined-Japanese-Patent No. 2-226149, the ester containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. are used preferably. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the amide monomer of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- meta Krylamide, diethylene triamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, etc. are mentioned. As an example of another preferable amide monomer, the amide which has the cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable, As such a specific example, it has two or more isocyanate groups in 1 molecule described in Unexamined-Japanese-Patent No. 48-41708, for example. The vinylurethane compound etc. which contain 2 or more polymerizable vinyl groups in 1 molecule obtained by adding the vinyl monomer containing the hydroxyl group represented by following General formula (V) to a polyisocyanate compound are mentioned.

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. )

Moreover, urethane acrylates as described in Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, Japanese Patent Application Laid-Open No. 2-16765, and Japanese Patent Publication No. 58-49860 Also preferred are urethane compounds having an ethylene oxide-based skeleton described in JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418. In addition, addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 are used. By doing this, the photopolymerizable composition which is very excellent in the photosensitive speed can be obtained.

As other examples, polyester acrylates, epoxy resins and the like described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting methacrylic acid. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, Unexamined-Japanese-Patent No. 1-40336, and the vinyl of Unexamined-Japanese-Patent No. 2-25493 are mentioned. Phosphonic acid type compounds etc. are mentioned. Moreover, in some cases, the structure containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-22048 is used preferably. See also Journal of the Adhesion Society of Japan Vol. 20, No. Photocurable monomers and oligomers described in 7,300 to 308 pages (1984) can also be used.

About these polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a final sensing material. For example, it selects from the following viewpoints.

In terms of sensitivity, a structure having a high content of unsaturated groups per molecule is preferable, and in most cases, a bifunctional or higher function is preferable. Moreover, in order to raise the intensity | strength of a coloring image part, ie, the photosensitive coloring composition layer, a trifunctional or more than trifunctional thing is good. Moreover, the method of adjusting both sensitivity and intensity | strength by using together the thing of another functional water and / or another polymerizable group (for example, acrylic acid ester, methacrylic acid ester, a styrene type compound, and a vinyl ether type compound) is also effective. It is preferable to use the compound containing two or more (meth) acrylic acid ester structures from a viewpoint of hardening sensitivity, It is more preferable to use the compound containing three or more, It is preferable to use the compound containing four or more Most preferred. Moreover, it is preferable to contain an EO modified body from a 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 strength.

The addition and use of addition polymer compounds are also important factors for compatibility and / or dispersibility with other components (eg, binder polymers, initiators, colorants (pigments or dyes, etc.)) in the photosensitive coloring composition layer. For example, compatibility may be improved by using a low-purity compound and using 2 or more types together. Moreover, a specific structure can also be selected for the purpose of improving adhesiveness with a board | substrate.

From the above viewpoints, bisphenol A diacrylate, bisphenol A diacrylate EO modified substance, trimetholpropane triacrylate, trimetholpropane tri (acryloyloxypropyl) ether, trimetholethane triacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, Sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, dipentaerythritol hexaacrylate EO modified, etc. Preferred examples are given. Moreover, as a commercial item, urethane oligomer UAS-10, UAB-140 [made by Nippon Seishi Chemical Co., Ltd.], DPHA [made by Nippon Kayaku Co., Ltd.], UA-306H, UA-306T, UA-306I, AH-600, T-600 And AI-600 (manufactured by Kyoeisha Kagaku Kogyo Co., Ltd.) are preferred.

Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, As a pentaerythritol tetraacrylate EO modified body, dipentaerythritol hexaacrylate EO modified body, and a commercial item, DPHA (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 And AI-600 (manufactured by Kyoeisha Kagaku Kogyo Co., Ltd.) are more preferable.

It is preferable that content of (C-1) polymeric compound is 5-55 mass% in the total solid in the photosensitive coloring composition layer of this invention, It is more preferable that it is 10-50 mass%, It is 15-45 mass% More preferred.

(D) photoinitiator

It is preferable that the photosensitive coloring composition of this invention contains the (D) photoinitiator.

The said photoinitiator is a compound which decomposes | disassembles with light, and starts and promotes superposition | polymerization of the said (C-1) polymeric compound, It is preferable to have absorption in the area | region of wavelength 300-500 nm. In addition, the said photoinitiator can be used individually or in combination of 2 or more types.

As said photoinitiator, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, an azide compound, a metallocene, for example A compound, a hexaaryl biimidazole compound, an organic boric acid compound, a disulfonic acid compound, an oxime ester compound, an onium salt compound, an acyl phosphine (oxide) compound is mentioned.

Specific examples of the organic halogenated compound include Wakabayashi et al., "Bull Chem. Soc Japan '' 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Japanese Patent Laid-Open No. 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 62-58241, Japanese Patent Laid-Open No. 62-212401, Japanese Patent Publication The compound of Unexamined-Japanese-Patent No. 63-70243, Unexamined-Japanese-Patent No. 63-298339, MPHutt "Journal of Heterocyclic Chemistry" 1 (No 3), (1970), etc. are mentioned, Especially, a trihalomethyl group And an sazole trisazine compound in which is substituted.

As an example of an s-triazine compound, More preferably, the s-triazine derivative which the at least 1 mono-, di-, or tri-halogen substituted methyl group couple | bonded with the s-triazine ring is mentioned, As a specific 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 (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy Phenyl) -4,6-bis (trichloromethyl) -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 (trichloro Rommethyl) -s-triazine, 2-styryl-4 , 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxysty Ryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-nathoxy Naphthyl) -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-tri Azine, 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, and the like.

Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole and 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodia Sol, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, and 2-trichloromethyl-5- (4-styryl) styryl-1,3 And 4-oxodiazole.

Examples of the carbonyl compound include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone Benzophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropane, 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-morpholinophenyl) -butanone-1, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Acetophenone derivatives such as oxides, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, and 2-benzyl-2-dimethylamino-4-morpholinobutyllophenone, thioxanthone, 2- Ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-di Thioxanthone derivatives, such as ethyl thioxanthone and 2, 4- diisopropyl thioxanthone, and benzoic acid ester derivatives, such as p-dimethylaminobenzoic acid ethyl and p-diethylaminobenzoic acid ethyl, etc. are mentioned.

As an example of a ketal compound, benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl ethyl acetal, etc. are mentioned.

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-arc And di (9-acridinyl) alkanes such as 1,11-di (9-acridinyl) undecane and 1,12-di (9-acridinyl) dodecane. have.

Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylper Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzenehydroperoxide, 2,5-dimethylhexane-2,5- Dihydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, tert-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane , 2,5-oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethylperox CDicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbo Nitrate, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxyneodecanoate, tert-butylperoxyoctanoate, tert-butylperoxy laurate, tertiary 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-butylperoxy dihydrogen 2phthalate), and carbonyldi (t-hexylperoxy dihydrogen 2 Phthalate) etc. are mentioned.

As an example of an azo compound, the azo compound etc. which were described in Unexamined-Japanese-Patent No. 8-108621 are mentioned.

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

Examples of azide compounds include the organic azide compounds described in US Pat. No. 2848328, US Pat. No. 2852379, and US Pat. No. 2940853, 2,6-bis (4-azidebenzylidene) -4-ethyl. Cyclohexanone (BAC-E) etc. are mentioned.

As an example of a metallocene compound, Unexamined-Japanese-Patent No. 59-152396, Unexamined-Japanese-Patent No. 61-151197, Unexamined-Japanese-Patent No. 63-41484, Unexamined-Japanese-Patent No. 2-249, Unexamined-Japanese-Patent No. Various titanocene compounds described in JP-A-2-4705 and JP-A-5-83588, for example, 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-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Methylcyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetra Roofen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, and Japanese Patent Laid-Open No. 1-304453; and The iron-arene complex of Unexamined-Japanese-Patent No. 1-152109, etc. are mentioned.

As an example of a hexaaryl biimidazole compound, the various compound described in each specification, such as Unexamined-Japanese-Patent No. 6-29285, US Patent 3,479,185, 4,311,783, 4,622,286, is mentioned, Examples include 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o -Chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5, 5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, etc. are mentioned. Can be.

As an example of an organic borate compound, Unexamined-Japanese-Patent No. 62-143044, Unexamined-Japanese-Patent No. 62-150242, Unexamined-Japanese-Patent No. 9-188685, Unexamined-Japanese-Patent No. 9-188686, Unexamined-Japanese-Patent No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, and Kunz, Martin " Organic borate described in Rad Tech '98. Proceeding April 19-22, 1998, Chicago "and the like, Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, and Japanese Patent Laid-Open No. 6-175561 The organoboron sulfonium complex or organoboron oxosulfonium complex described in the publication, the organic boron iodonium complex described in JP-A-6-175554, and JP-A-6-175553, JP-A-9- Organoboron force described in Japanese Patent No. 188710 Ium complex, and Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785, Japanese Patent Laid-Open No. 7-140589, Japanese Patent Laid-Open No. 7-306527, and Japanese Patent Laid-Open No. 7 Organic boron transition metal coordination complexes, such as -292014, etc. are mentioned.

As an example of a disulfone compound, the compound etc. which are described in Unexamined-Japanese-Patent No. 61-166544, Unexamined-Japanese-Patent No. 2002-328465, etc. are mentioned.

As an example of an oxime ester compound, J.C.S. Perkin II (1979) 1653-1660, J.C.S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and the compounds described in Japanese Patent Application Laid-Open No. 2000-66385, and Japanese Patent Application Laid-Open No. 2000-80068, and Japanese Patent Publication 2004 The compound etc. which were described in -534797 are mentioned. As a specific example, Irgacure OXE-01, OXE-02, etc. made from Chiba Specialty Chemicals are preferable.

Examples of onium salt compounds include S.I. Schlesinger, Photogr. Sci. Diazonium salts described in Eng., 18,387 (1974), and TSBal et al, Polymer, 21,423 (1980), ammonium salts described in US Pat. No. 4,069,055, and Japanese Patent Application Laid-open No. Hei 4-365049, US Pat. The phosphonium salts described in 4,069,055 specification and 4,069,056 specification, European Patent No. 104,143, Japanese Patent Application Laid-Open No. 2-150848, and Japanese Patent Application Laid-Open No. 2-296514. Iodonium salt etc. are mentioned.

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

Examples of sulfonium salts that can be preferably used in the present invention include European Patent No. 370,693, Patent 390,214, Patent 233,567, Patent 297,443, Patent 297,442, Patent 4,933,377 and Patent 4,760,013. The sulfonium salt of each specification of the specification, 4,734,444 specification, 2,833,827 specification, German Patent No. 2,904,626 specification, 3,604,580 specification, and 3,604,581 specification is mentioned. It is preferable that this sulfonium salt is substituted by the electron-withdrawing group from the point of stability and sensitivity. It is preferable that the Hammett value of the electron-withdrawing group is larger than zero. As an example of a preferable electron withdrawing group, a halogen atom, a carboxylic acid, etc. are mentioned.

Moreover, as an example of another preferable sulfonium salt, the sulfonium salt which has one dentifier of a triaryl sulfonium salt has a coumarin structure or an anthraquinone structure, and has absorption in 300 nm or more. As an example of another preferable sulfonium salt, the sulfonium salt which triarylsulfonium salt has an aryloxy group or an arylthio group as a substituent, and has absorption in 300 nm or more is mentioned.

Moreover, as an example of an onium salt compound, J.V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), and J.V. Crivello et al, J. Polymer Sci., Polymer Chem. Selenium salts described in Ed., 17, 1047 (1979), and C.S. Wen et al, Teh, Proc. Conf. Rad. Onium salts, such as the arsonium salt as described in Curing ASIA, p478 Tokyo, Oct (1988), etc. are mentioned.

As an example of an acyl phosphine (oxide) compound, the monocure 819 by Chiba Specialty Chemicals Corporation, DAROCURE 4265, Darocure TPO, etc. are mentioned.

As an example of the (D) photoinitiator, from a viewpoint of exposure sensitivity, a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, the acyl phosphine type compound, the phosphine oxide compound, Metallocene compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyloxadia A sol compound and the 3-aryl substituted coumarin compound are mentioned.

More preferably, trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triarylimidazole dimer, onium compound, benzophenone compound, and acetophenone compound And at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is most preferred.

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

(E) solvent

The photosensitive coloring composition used for this invention can be prepared generally using a solvent.

Examples of the solvent include esters such as ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetic acid, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid, methoxyacetic acid butyl, ethoxyacetic acid methyl, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters, such as 3-oxy methyl propionate and 3-oxy ethyl ethyl (for example, methyl 3-methoxypropionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy) Ethyl propionate and the like); 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionic acid (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, and 2-methoxypropionic acid) Propyl, 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-e Ethoxy -2-methyl propionate etc.); 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 Agent, dipropylene glycol monomethyl ether acetate, dipropylene glycol n- propyl ether acetate, dipropylene glycol n- butyl ether acetate, tripropylene glycol n- butyl ether, and tripropylene glycol methyl ether acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, and propylene glycol mono n-butyl ether; And

Aromatic hydrocarbons such as toluene, xylene and the like.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, and 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 preferable.

A solvent may be used independently and may be used in combination of 2 or more type.

Other additives

Moreover, various well-known additives can further be used for the photosensitive coloring composition used for this invention according to the objective besides the said component.

Hereinafter, such an additive is described.

Dispersant

It is preferable that the photosensitive coloring composition in this invention contains a polymeric dispersing agent. This polymer dispersing agent is resin which has a weight average molecular weight in the range of 3,000-100,000. Moreover, it is preferable that acid value is 20-300 mg / g. Such specific polymer dispersing agent may only be called "dispersion resin" below.

The dispersion resin in the present invention may function as a dispersant of the pigment exemplified as the (A-1) colorant or as a dispersant of a light shielding agent (pigment for forming a black matrix) in a photosensitive deep color composition for forming a black matrix described later. Compound.

Since dispersion resin needs to have specific acid value, it is preferable that it is a high molecular compound which has an acidic group.

Examples of the polymer skeleton of the polymer compound include polymers of vinyl monomers, copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, and silicone polymers, and modified products or copolymers thereof. At least one selected from the group consisting of polyether / polyurethane copolymers, copolymers of polyether / vinyl monomer polymers, and the like (any of random copolymers, block copolymers, and graft copolymers). desirable. At least 1 sort (s) chosen from the group which consists of a polymer of a vinyl monomer, a copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, and these modified | denatured products or a copolymer is more preferable, The polymer of a vinyl monomer and the air of a vinyl monomer are more preferable. Coalition is particularly preferred.

Moreover, as a method of introducing an acidic group into the above-mentioned polymer skeleton, the method of copolymerizing the monomer containing an acidic group when superposing | polymerizing the said polymer skeleton, or the method of introducing the said polymer skeleton by polymer reaction after superposition | polymerization is mentioned, for example. Can be mentioned.

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, vinylbenzoic acid, styrenesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, monophosphate ( And a monomer obtained by reacting an alcoholic hydroxyl group-containing monomer such as meta) acryloylethyl ester or 2-hydroxyethyl methacrylate, and a cyclic acid anhydride such as maleic anhydride or phthalic anhydride.

The polymer compound having an acidic group may further contain a vinyl monomer component as a copolymerization component.

Examples of the vinyl monomer include, but are not particularly limited to, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and (meth) acrylamides. Drew, vinyl ether, ester of vinyl alcohol, styrene, (meth) acrylonitrile, etc. are mentioned.

Preferred examples of the "acidic group" include a carboxylic acid group, a sulfonic acid group, a monosulfate ester group, a phosphoric acid group, a monophosphate ester group, and a boric acid group, and a carboxylic acid group, a sulfonic acid group, a monosulfate ester group, a phosphoric acid group, and Monophosphate ester group is more preferable, and a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are especially preferable.

Moreover, it is also preferable that the photosensitive coloring composition in this invention contains the group which has a basic nitrogen atom for the improvement of dispersibility. Examples of the group having a basic nitrogen atom include an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , or -NR ⁹ R ¹⁰ ; wherein R ⁸ , R ⁹ , and R ¹⁰ each independently represent 1 to C 1. 20 alkyl groups, aryl groups having 6 or more carbon atoms, or aralkyl groups having 7 or more carbon atoms), guanidyl groups represented by the following formula (a1), or amidinyl groups represented by the following formula (a2) Can be.

R ¹¹ and R ¹² in the formula (a1) 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.

R ¹³ and R ¹⁴ in the formula (a2) 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 ; wherein R ⁸ , R ⁹ , and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group, or benzyl The guanidyl group represented by the said general formula (a1) (In formula (a1), R <^11> and R <^12> represents a C1-C10 alkyl group, a phenyl group, or a benzyl group each independently.), The said general formula (a2). Amidinyl group (R ¹³ and R ¹⁴ in formula (a2) each independently represents an alkyl group, phenyl group, or benzyl group having 1 to 10 carbon atoms); and 1 to 200 hydrogen atoms and 0 to 20 The group formed from the sulfur atoms of the dog is further contained, and these may be unsubstituted or may further have a substituent.

Other dispersants

The photosensitive coloring composition used for this invention can also use together the said dispersion resin and a conventionally well-known dispersing agent (pigment dispersing agent).

Examples of known dispersants (pigment dispersants) include polymer dispersants (e.g., polyamideamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic airs). Copolymer), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanolamine, and pigment derivatives.

Polymeric dispersants can also be classified from their structure into linear polymers, terminal modified polymers, graft polymers, and block polymers.

The polymeric dispersant is adsorbed on the surface of the pigment and acts to prevent reagglomeration. Therefore, a terminal modified polymer, a graft polymer, or a block polymer having an anchor portion to the pigment surface is mentioned as a preferable structure. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

As a specific example of the well-known dispersing agent (pigment dispersing agent) which can be used for this invention, Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 by BYK Chemie (Polymer copolymer), EFKA 4047, 4050, 4010, 4165 (polyurethane system), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 6220 made from EFKA (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), AJISPER PB821, PB822, product made by Ajinomoto Fine Techno Co., Ltd. (FLOWLEN) TG-710 (Kyoeisha Kagaku Corporation make) Oligomer), POLYFLOW No. 50E, No. 300 (acrylic copolymer), Disparon # 7004 (polyether ester) made by Kusumoto Kasei Co., Ltd., DA-703-50, DA-705, DA-725, emulgen (EMULGEN) 920 made by Kao Corporation , 930, 935, 985 (polyoxyethylene nonylphenyl ether), acetamine (ACETAMIN) 86 (stearylamine acetate), SOLSPERSE 5000 (phthalocyanine derivative) made by Lubrizol, 22000 (azo pigment derivative) , 13240 (polyester amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer), Nikko (NIKKOL) T106 (polyoxyethylene sorbitan) Monooleate), MYS-IEX (polyoxyethylene monostearate), etc. are mentioned.

The above-mentioned well-known dispersing agent can be used in the range of 10-100 mass% with respect to dispersion resin, ie, a dispersing agent / dispersion resin = 1 / 10-1 / 1 (equivalent amount) as needed.

Surfactants

When the pigment concentration is increased, the thixotropy of the coating liquid is generally large, so that the film thickness variation after the formation of the photosensitive coloring composition layer (color layer coating film) is likely to occur by applying or transferring the photosensitive coloring composition onto the substrate. Moreover, especially in the formation of the photosensitive coloring composition layer (color layer coating film) by the slit coat method, it is important to level until the coating liquid for photosensitive coloring composition layer formation dries, and to form the coating film of uniform thickness. For this reason, it is preferable that the said photosensitive coloring composition contains a suitable surfactant. As an example of the said surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned.

As an example of surfactant for improving applicability | paintability, a nonionic surfactant, a fluorine-type surfactant, a silicone type surfactant, etc. are mentioned.

Examples of nonionic surfactants include polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers, and poly Oxypropylene alkylaryl esters, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters.

As a specific example of a nonionic surfactant, Polyoxyalkylene glycol, such as polyoxyethylene glycol and polyoxypropylene glycol; Polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene polythiylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polytyrylated ether and polyoxyethylene nonylphenyl ether; Polyoxyalkylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Sorbitan fatty acid esters; And polyoxyalkylene sorbitan fatty acid esters.

As these new specific examples, Adeka PLURONIC series, Adekanol series, TETRONIC series (above ADEKA Co., Ltd. make), Emulgen series (EMULGEN series) , Leopold series (RHEODOL series) (above, Kao Corporation), Ereninol series (ELEMINOL series), Noni Falls series (NONIPOL series), Octapol series (OCTAPOL series), Dodecapol series (DODECAPOL series), New pole series (NEWPOL series) [product made in Sanyokasei Co., Ltd.], pioneer series (PIONIN series) [product made by Takemoto Yushi Corporation], Nissan NBION series (NISSAN NONION series) [product made by Nippon Yushi Corporation] Etc. can be mentioned. These commercially available can be used suitably. The preferred HLB (Hydrophile-Lipophile Balance) value is 8-20, more preferably 10-17.

As an example of a fluorochemical surfactant, the compound which has a fluoroalkyl group or a fluoroalkylene group in the site | part of at least any one of a terminal, a main chain, and a side chain is mentioned.

As an example of a specific commercial item, Megapack (MEGAFAC) F142D, copper F172, copper F173, copper F176, copper F177, copper F183, copper 780, copper 781, copper R30, copper R08 (made by Dainippon Ink Co., Ltd.), fluoride (FLUORAD) FC-135, East FC-170C, East FC-430, East FC-431 (made by Sumitomo 3M Co., Ltd.), SURFLON S-112, East S-113, East S-131, East S-141, East S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 [Asahi Glass Co., Ltd.] ], EFTOP EF 351, 352, 801, 802 (made by JEMCO Corporation), etc. are mentioned.

As an example of a silicone type surfactant, Toray Silicone DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF- 8428, copper DC-57, copper DC-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 [more, Momentive Performance Materials Japan] etc. are mentioned.

The amount of these surfactants is preferably 5 parts by mass or less, and 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 in coating drying tends to occur, and smoothness tends to deteriorate.

Moreover, when promoting alkali solubility of an uncured part and for further improvement of the developability of a photocurable composition, you may add organic carboxylic acid, Preferably low molecular weight organic carboxylic acid whose weight average molecular weight is 1000 or less. Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capric acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azeline acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Phenylacetic acid, phenoxyacetic acid, methoxyphenoxyacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, coumalic acid, umbelic acid And other carboxylic acids.

Alkoxysilane Compound

The photosensitive coloring composition used for this invention may further contain an alkoxysilane compound and the silane coupling agent among them from the viewpoint of adhesiveness improvement with a board | substrate.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group chemically bondable with an inorganic material, and as an example of a more preferred silane coupling agent, a (meth) acryl is exhibited by interacting or bonding with an organic resin to show affinity. It is preferable that they are loyl, phenyl, mercapto, and epoxysilane, and (meth) acryloylpropyl trimethoxysilane is mentioned as an especially preferable example.

It is preferable that it is the range of 0.2-5.0 mass% in the total solid in the photosensitive coloring composition layer used for this invention, and, as for the addition amount when using a silane coupling agent, 0.5-3.0 mass% is more preferable.

Notary sensitizer

It is also preferable that the photosensitive coloring composition used for this invention contains a sensitizer as desired. In the present invention, the sensitizer has an action of further improving the sensitivity of the sensitizing dye and / or the initiator to the actinic radiation, or inhibiting the inhibition of polymerization of the polymerizable compound by oxygen.

Examples of such a sensitizer include amines such as MR Sander et al., Journal of Polymer Society, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, The compound described in Research Disclosure 33825, etc. are mentioned, As a specific example, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethyl aniline, p-methylthio dimethylaniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides, for example, a thiol compound disclosed in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, Japan The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned. As a specific example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H)-quinazoline, (beta) -mercaptonaphthalene, etc. are mentioned. .

In addition, examples of the sensitizer include an amino acid compound (for example, N-phenylglycine), an organometallic compound (for example, tributyl tin acetate, and the like) described in JP-A-48-42965, and JP-A. Hydrogen donor of the 55-34414, the sulfur compound of Unexamined-Japanese-Patent No. 6-308727 (for example, trithiane etc.), etc. are mentioned.

As for content of these co-sensitizers, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the hardening rate by the balance of a polymerization growth rate and a chain transfer, and is 1-25 mass% The range of is more preferable, and the range of 0.5-20 mass% is further more preferable.

Polymerization inhibitor

In the present invention, during the preparation or storage of the photosensitive coloring composition, it is preferable to add a small amount of thermal polymerization inhibitor to the photosensitive coloring composition in order to prevent unnecessary thermal polymerization of the compound having a polymerizable ethylenically unsaturated double bond. .

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'-thio Bis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine first cerium salt, etc. are mentioned. have.

As for the addition amount of a thermal-polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass in the photosensitive coloring composition layer. If necessary, in order to prevent the inhibition of polymerization by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added, and may be localized on the surface of the photosensitive layer in the drying process after application. 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

In addition, in this invention, in order to improve the physical property of the photosensitive coloring composition layer, you may add an inorganic filler or a plasticizer, or a sensing agent which can improve the ink buildability of the photosensitive layer surface.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine and the like. When using a binder, 10 mass% or less plasticizer can be added with respect to the total mass of a compound and an binder which have an ethylenically unsaturated double bond.

By using the above-mentioned component, the photosensitive coloring composition in this invention hardens with high sensitivity, and storage stability also becomes favorable. Moreover, high adhesiveness to a board | substrate is shown. Therefore, the photosensitive coloring composition containing the said various component can be used suitably for a color filter.

Photosensitive thickening composition

It is preferable that the photosensitive deepening composition used for this invention contains (A-2) light-shielding agent, (B) binder polymer, (C-2) polymeric compound, (D) photoinitiator, and (E) solvent, and is necessary. It may also contain other additives such as dispersants or surfactants.

(A-2) Shading Agent

Examples of the light-shielding agent (A-2) include carbon black, titanium black, metal fine particles, metal oxides, and sulfide fine particles in addition to the above-mentioned (A-1) colorant. Especially, carbon black which is excellent in the balance of light-shielding property and cost is especially preferable.

These are used individually or in combination of multiple types as needed. Examples thereof include carbon black alone, a mixture of organic pigments, and a combination of carbon black and organic pigments.

As a material for light shielding, at least 2 or more types of pigments have been used together as a black coloring agent so that a visible light area may be shielded conventionally. As an example of these pigments, the pigment of Unexamined-Japanese-Patent No. 2005-17716 [0038]-[0040], and the Unexamined-Japanese-Patent No. 2005-17521-[0080]-[0088] is mentioned, The light-shielding using these pigments is mentioned. The formation of the layer is disclosed in Japanese Patent Laid-Open No. 7-271020 and the like.

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 2006-154849 and the like, carbon black, titanium black, graphite, or the like are preferable light shielding materials. Has been developed. In the present invention, carbon black is a preferred example of the light shielding material from the viewpoint of light shielding properties and cost.

As an example of carbon black, pigment black 7 (carbon black) is preferable. As carbon black, for example, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # made by Mitsubishi Kagaku 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, DIABLACK A, DIA BLACK N220M, DIA BLACK N234 , Diamond black I, diamond black LI, diamond black II, diamond black N339, 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; Carbon black Color Black FW200, Color Black FW2, Color Black FW1, Color Black FW18, Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, Printex U, Printex V, Printex 140U, Printex 140V, Printex 35; Carbon black REGAL 400, REGAL 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, BLACK PEARLS 1400; Carbon black SUNBLACK 900, Copper 910, Copper 930, Copper 960, Copper 970 by Asahi Carbon, etc. are mentioned. In addition, a coating of these carbon blacks with a high molecular compound in order to increase the electrical resistance is also preferable. The preferred size of the discrete particles of these carbon blacks is 10 nm to 100 nm, more preferably 10 nm to 50 nm.

(C-2) Polymerizable Compound

As a (C-2) polymeric compound in the photosensitive deepening composition for black-matrix formation, the (C-1) polymeric compound used in the said photosensitive coloring composition is also mentioned as a preferable thing, Especially the compound shown below is desirable.

As a polymeric compound in the photosensitive deepening composition, it is preferable that it is a monomer or oligomer which has two or more ethylenically unsaturated double bonds and adds polymerization by irradiation of light. As an example of such a monomer and an oligomer, the compound which has an ethylenically unsaturated group which can be at least 1 addition polymerization in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is mentioned. As the specific example, Monofunctional acrylate and monofunctional methacrylate, such as polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimetholethane triacrylate, trimetholpropane tri (meth) acrylate, trimetholpropane diacrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) Acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxy ethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; And polyfunctional acrylates or polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimetholpropane or glycerin and then (meth) acrylated.

Moreover, an acidic polyfunctional photocurable compound is also mentioned as a preferable example. Examples of the acidic polyfunctional photocurable compound include (1) a compound obtained by introducing a carboxyl group by modifying a monomer or oligomer having three or more photocurable functional groups together with a hydroxyl group to a dibasic acid anhydride, (2) three or more together with a hydroxyl group Concentrated sulfuric acid or fuming a compound obtained by introducing a carboxyl group by adding a glycidyl group or a compound having an isocyanate group and a COOH group to a monomer or oligomer having a photocurable functional group, or (3) an aromatic compound having three or more photocurable functional groups. The compound etc. which were obtained by introduce | transducing a sulfonic acid group by denaturation with sulfuric acid are mentioned. 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. Acidic polyfunctional photocurable compound As a preferable example, the compound represented by the following general formula (i) or general formula (ii) is mentioned. In addition, in general formula (iii) and general formula (ii), when T or G is an oxyalkylene group, the terminal at the side of a carbon atom couple | bonds with R, X, or W. Moreover, as shown to FIG.

In the general formula (i), R represents an acryloyloxy group in a (meth) acrylate, X represents a -COOH group, or -OPO ₃ H _2. T represents an oxyalkylene group, and carbon number of an alkylene group is 1-4 here. n is 0-20.

In general formula (ii), W is synonymous with R or X in general formula (iii), and three or more W out of six W is synonymous with R. G is synonymous with T in General formula. Z represents -O- or -OC = ONH (CH ₂ ) qNHCOO-. p is 0-20 and q is 1-8. Two or more R, T, G, and W in one molecule may be same or different, respectively.

As an example of the commercial item of the acidic polyfunctional photocurable compound represented by General formula (i) and General formula (ii), TO-756 which is a carboxyl group-containing trifunctional acrylate made by Toagosei Co., Ltd., and a carboxyl group-containing 5-functional acrylate Phosphorus TO-1382 etc. are mentioned.

As another example, the urethane acrylates described in Unexamined-Japanese-Patent No. 48-41708, Unexamined-Japanese-Patent No. 50-6034, and Unexamined-Japanese-Patent No. 51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and polyfunctional methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. In the above, trimetholpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the carboxyl group-containing 5-functional acrylate This is preferred. In addition, "polymerizable compound B" described in Unexamined-Japanese-Patent No. 11-133600 is also a preferable example.

It is preferable that content of the (C-2) polymeric compound in the photosensitive deepening composition used for forming a black matrix is 5-50 mass% in the total solid of the photosensitive deepening composition layer, and it is 7-40 mass% More preferably, it is still more preferable that it is 10-35 mass%.

The (B) binder polymer, (D) polymerization initiator, (E) solvent, other additives, etc. which are used for the photosensitive deepening composition are the same as those in the photosensitive coloring composition for coloring pattern formation mentioned above, and its preferable content is also the same.

Color filter

The color filter of this invention is a color filter manufactured by the manufacturing method of the color filter of this invention, has an overlap part which a black matrix and a coloring pattern overlap, and the length in the width direction of the black matrix of the said overlap part is 1.0 micrometer-12 [Mu] m.

Using the photosensitive coloring composition and the photosensitive deepening composition, the color filter of the present invention manufactured by the method for producing a color filter of the present invention has a low height of the ridge and is also suitable for the length of the overlap and a high quality display. To make it possible. It is preferable that the length of the said overlap part is 1.0 micrometer-12 micrometers, and the height of the said bump is 0.50 micrometer or less.

LCD Display

The liquid crystal display device of the present invention is a liquid crystal display device provided with the color filter of the present invention. Therefore, a high quality image can be displayed.

The spacer can use the manufacturing method by coating or the manufacturing method by transfer suitably. The manufacturing method by application | coating is preferable at a point with a simple process. The manufacturing method by transfer is preferable at the point that the uniformity of a spacer height is good. About the manufacturing method by transcription | transfer, the method of Unexamined-Japanese-Patent No. 2008-146018 is especially preferable.

For the definition of the display device and the explanation of each display device, for example, "Electronic display device (by Akio Sasaki, issued by Kokyocho Sakai Co., Ltd., 1990)", "Display device (by Ibuki Sumiaki, by Sankyo Show Co., Ltd.) Issued in 1989). Moreover, about a liquid crystal display device, it describes in the "next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo-cho Sakai Co., 1994)." There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in the said "next-generation liquid crystal display technology."

The present invention is particularly effective in the liquid crystal table market value of the color TFT (Thin Film Transistor) system. About the liquid crystal display device of a color TFT system, it describes in a "color TFT liquid crystal display (Kyoritsu Shooting Co., Ltd. 1996 issuance), for example. In addition, the present invention provides a liquid crystal display device having an enlarged viewing angle such as a lateral electric field driving method such as IPS (In-Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a super-twisted nematic (STN), and a TN. (Twisted Nematic), VA (Vertical Alignment), OCS (On Chip Spacer), FFS (Fringe Field Switching), R-OCB (Reflective Optically Compensated Bend) and the like. These methods are described, for example, on page 43 of `` Electro-Luminescence (EL), Plasma Display Panel (PDP), LCD Display-Latest Trends in Technology and Markets '' (Published in 2001 by Toray Research Center). have.

In addition to the color filter, the liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle guarantee film, and the like. The board | substrate with a light shielding film of this invention is applicable to the liquid crystal display device comprised from these well-known members.

For these members, for example, the market of '94 liquid crystal display peripheral materials and chemicals (Kenta Shima CMC, 1994), the current status and future prospects of the 2003 liquid crystal related market (the lower volume) (Omote) Ryokichi, Fuji Chimera Souken, 2003 issue).

Backlighting is described in SID Meeting Digest 1380 (2005) (A.Konno et. Al), pages 18-24 (Shima Yasuhiro), pages 25-30 (Yagi Takaaki), etc. of the December 2005 issue of the monthly display. .

The color filter of the present invention can realize high contrast when combined with a three-wavelength tube of a conventionally known cold cathode tube. Further, by using the red, green, and blue LED light sources (RGB-LEDs) as backlights, it is possible to provide a liquid crystal display device having high luminance and high color reproducibility.

On the other hand, the performance required for the liquid crystal display device is an improvement in the response speed of the image. In order to improve the response speed, the alignment speed of the liquid crystal is improved. On the other hand, from the structure surface of a cell, the thickness reduction of a liquid crystal layer requires a cost reduction image. Another technique required for reducing the thickness of the liquid crystal layer is to reduce the orientation disturbance of the liquid crystal at the boundary between the colored pixel and the black matrix. For this reason, it is required to reduce the elevation at the boundary between the colored pixel and the black matrix.

The color filter manufactured by the manufacturing method of the color filter of this invention has the cross-sectional shape of the photosensitive deepening composition layer for black-matrix formation after image development which is nearly vertical, and the photosensitive coloring composition layer and black for formation of a coloring pattern (color pixel). The length of the overlap portion of the matrix is 1.0 to 12 µm, and the ridges can be made small.

As described above, the color filter of the present invention has a small bump, so that the alignment disturbance of the liquid crystal in the overlap portion can be reduced, and the visibility at the time of image display is also improved. By using the color filter of the present invention in the liquid crystal display of the present invention, it is possible to flatten the overlapping portion with the black matrix of each colored pixel, and when the flatness is good, the liquid crystal layer is thinned or polished before laying the transparent electrode ITO. In addition, it is not necessary to provide a planarization layer, which contributes to rationalization of the process, cost reduction, and mass productivity.

EXAMPLE

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, reagents, ratios, instruments, operations, and the like shown in the following examples can be changed as appropriate without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below. In addition, unless otherwise indicated in a following example, "%" and "part" show the "mass%" and the "mass part", and a molecular weight shows a weight average molecular weight. In addition, "wt%" shows the "mass%."

Example 1

1. Preparation of the photosensitive deepening composition

Preparation of Carbon Black Dispersion (K-1)

The carbon black dispersion (K-1) was prepared by the following prescription.

Carbon black (color black FW2 made by Degussa)... Part 26.7

Dispersant [Kusmoto Kasei Disparon DA7500 (acid number 26; amine number 40)]

                                                  … Part 3.3

Benzyl methacrylate / methacrylic acid copolymer

  (= 72/28 [molar ratio] copolymer, molecular weight 30,000, 50 mass% solution of propylene glycol monomethyl ether acetate)… Part 10

Propylene glycol monomethyl ether acetate... 60 copies

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The resultant mixed solution was subjected to microdispersion treatment for 8 hours using a bead disperser (trade name: DESPERMAT, manufactured by GETZMANN (VMA-GETZMANN GMBH)) using 0.3 mm zirconia beads to obtain a carbon black dispersion (K-1). .

Using the obtained carbon black dispersion (K-1), the photosensitive deep color composition coating liquids CK-1, CK-3, and CK-4 were prepared by the prescription of Table 1 below. The numerical value of Table 1 shows mass ratio.

The detail of each component of Table 1 is as follows.

Resin solution C-2: Benzyl methacrylate / methacrylic acid copolymer (= 85/15 [molar ratio] copolymer, Mw 10,000, 50 wt% solution of propylene glycol monomethyl ether acetate)

UV-curable resin C-3: Product name Cyclomer P ACA-250 Daicel Kagaku Kogyo Co., Ltd. make [Acrylic copolymer, propylene glycol monomethyl ether acetate solution which has alicyclic group, COOH group, and acryloyl group in a side chain] (Solid content: 50% by mass)]

Polymerizable compound C-5: A mixture of 60 to 40 (mass ratio) of KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. and KAYARAD R684 manufactured by Nippon Kayaku Co., Ltd.

Initiator C-7: Product name "OXE-02" manufactured by Chiba Specialty Chemicals

Surfactant C-8: Product name "Megapack R30" Dainippon Ink & Chemicals Co., Ltd. make

Solvent: PGMEA = propylene glycol monomethyl ether acetate

        EEP = 3-Ethoxyethyl Propionate

2. Formation of Black Matrix by Application

Photosensitive deep color composition layer forming process

The film thickness after post-baking the obtained photosensitive deepening composition CK-1 using the slit coater (model number HC6000, the product made by Hirata Giko Co., Ltd.) to the cleaned glass substrate (Millenium (MILLENIUM) made by Corning Corporation) 1.2 The space | interval between a slit and a glass substrate, and discharge amount were adjusted so that it might become micrometer, and it apply | coated at the application | coating speed of 120 mm / sec.

Prebaking Process and Exposure Process

Subsequently, heating (prebaking process) was performed at 80 degreeC for 120 second using the hotplate, and it exposed at 60 mJ / cm <2> using the proximity type exposure machine (the model number LE5565A, the Hitachi High-Technologies company).

Developing Process

Then, it developed with the horizontal conveyance developing apparatus. Namely, shower with 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by Fujifilm Electronics Material Co., Ltd.) (that is, a diluent containing 1 part by mass of CDK-1 and 99 parts by mass of pure water; 24 ° C). The pressure was set to 0.15 MPa, developed for 37 seconds, washed with pure water, and the black matrix after development was obtained.

As a result of photographing the cross-sectional shape of the black matrix using SEM (Scanning Electron Microscope), the cross-sectional shape was confirmed. As a result, the lower end of the black matrix was in a forward taper shape of approximately 3 μm in the width direction of the black matrix. In addition, the position of the lower end with respect to the upper end in a following example and a comparative example is shown in Table 6 (it describes as "distance of an upper end-a lower end" in Table 6).

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 near the center of the long side of the lattice of the black matrix.

Baking process

Subsequently, the post-baking process was performed for 40 minutes in the clean oven at 220 degreeC, and the lattice-shaped black matrix whose opening of a colored pixel formation area is 90 micrometers x 200 micrometers, the thickness of a black matrix is 1.2 micrometers, and the line width of a black matrix is about 25 micrometers. A substrate was formed.

It was 4.2 when the optical density (OD) of the completed black matrix was measured using X-Rite 361T (V) (made by Sakata Ink Engineering Co., Ltd.).

3. Preparation of Photosensitive Coloring Composition

3-1. Preparation of photosensitive coloring composition coating liquid CR-1 for red (R)

The dispersion (R-1) for red (R) was prepared with the following prescription.

Pigment Red 254 (average particle diameter 43 nm in SEM observation). Part 11

Pigment Red 177 (average particle diameter 58 nm in SEM observation). Part 4

Dispersion resin A-3 below. Part 5

Dispersant (brand name: Disperbyk-161, BIC Chem Corporation)

(30% solution of propylene glycol monomethyl ether acetate) Part Three

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 mass%)). Part 9

Solvent B: propylene glycol monomethyl ether acetate... Part 68

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The obtained mixed solution was microdispersed for 4 hours using the bead disperser (brand name: dispermat, the product made by GETZMANN) using 0.3 mm zirconia beads, and the dispersion liquid for red (R) (R-1) was obtained. The average particle diameter was 36 nm as observed by SEM.

The photosensitive coloring composition coating liquid CR-1 for red (R) was prepared by the following prescription using the obtained dispersion (R-1) for red (R).

· Dispersion (R-1) for red (R). 100 copies

Epoxy resin: (brand name EHPE3150 Daicel Kagaku Kogyo Co., Ltd.) Part Two

Polymerizable compound: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Part 8

Polymerization initiator: 4- (o-bromo-p-N, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine. chapter 1

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

                                                            … chapter 1

Polymerization initiator: diethyl thioxanthone... 0.5 part

Polymerization inhibitor: p-methoxyphenol... 0.001 copies

Fluorine-based surfactant (brand name: MEGAFAC R30 Dainippon ink Kagaku Kogyo Co., Ltd.)

                                                            … 0.01 part

Nonionic surfactant (trade name: manufactured by Tetronic R150 ADEKA Corporation)... 0.2 part

Solvent: Propylene glycol n-butyl ether acetate Part 30

Solvent: Propylene glycol monomethyl ether acetate 100 copies

The said component was mixed and stirred, and the photosensitive coloring composition coating liquid CR-1 for red (R) was obtained.

3-2. Preparation of photosensitive coloring composition coating liquid CG-1 for green (G)

The dispersion (G-1) for green (G) was prepared by the following prescription.

Pigment Green 36 (average particle diameter 47 nm in SEM observation). Part 11

Pigment Yellow 150 (average particle diameter 39 nm in SEM observation). Part 7

Dispersion resin A-3 below. Part 5

Dispersant (brand name: Disperbyk-161, 30% solution made by BIC Chem) Part Three

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%)) Part 11

Solvent: Propylene glycol monomethyl ether acetate 70 copies

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The obtained mixed solution was subjected to microdispersion treatment for 8 hours using a bead disperser (trade name: Dispermat, manufactured by GETZMANN Corporation) using 0.3 mm zirconia beads to obtain a dispersion (G-1) for green (G).

The photosensitive coloring composition coating liquid CG-1 for green (G) was prepared by the following prescription using the obtained dispersion (G-1) for green (G). When observed again by SEM, the average particle diameter was 32 nm.

· Dispersion (G-1) for green (G). 100 copies

Epoxy resin: (product name EHPE3150 Daicel Kagaku Kogyo Co., Ltd.) Part Two

Polymerizable compound: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Part 8

Polymerizable compound: tetra (ethoxyacrylate) of pentaerythritol; Part Two

Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolantriazine... Part Two

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

                                                            … chapter 1

· Polymerization initiator: diethyl thioxtone 0.5 part

Polymerization inhibitor: p-methoxyphenol... 0.001 copies

Fluorine-based surfactant (brand name: MEGAFAC R08 Dainippon ink Kagaku Kogyo Co., Ltd.)

                                                            … 0.02part

Nonionic surfactant (trade name: emulgen A-60 KAO Co., Ltd.); 0.5 part

Solvent: Propylene glycol monomethyl ether acetate 120 copies

Solvent: Propylene glycol n-propyl ether acetate Part 30

The said composition was mixed and stirred, and the photosensitive coloring composition coating liquid CG-1 for green (G) was obtained.

3-3. Preparation of photosensitive coloring composition coating liquid CB-1 for blue (B)

The dispersion (B-1) for blue (B) was prepared by the following prescription.

Pigment Blue 15: 6 (average particle diameter 55 nm in SEM observation). Part 14

Pigment Violet 23 (average particle diameter 61 nm in SEM observation). chapter 1

Dispersion resin A-3 below. Part 5

Dispersant (brand name: Disperbyk-161, 30% solution made by BIC Chem) Part Three

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer

  (= 80/20 [molar ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate (solid content: 50 mass%)). Part 4

Solvent: Propylene glycol monomethyl ether acetate Part 73

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The obtained mixed solution was microdispersed for 4 hours using the bead disperser (brand name: dispermat, the product made by GETZMANN) using 0.3 mm zirconia beads, and the dispersion liquid for blue (B) (B-1) was obtained. When observed again with an SEM, the average particle diameter was 39 nm.

The photosensitive coloring composition coating liquid CB-1 for blue (B) was prepared by the following prescription using the obtained dispersion (B-1) for blue (B).

· Dispersion (B-1) for blue (B). 100 copies

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%)) Part 7

Epoxy resin: (product name Celoxide 2080 Daicel Kagaku Kogyo Co., Ltd.)

                                                            … Part Two

UV curable resin: (brand name cyclomer P ACA-250 Daicel Kagaku Kogyo KK)

(Acrylic copolymer having alicyclic group, COOH group, and acryloyl group in side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)) Part 4

Polymerizable compound: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Part 12

Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyl oxime) ethanone Part Three

Polymerization inhibitor: p-methoxy phenol. 0.001 copies

Fluorine-based surfactant (brand name: MEGAFAC R08 Dainippon ink Kagaku Kogyo Co., Ltd.)

                                                            … 0.02part

Nonionic surfactant (trade name: emulgen A-60 KAO Co., Ltd.); 1.0 part

Solvent: 3-ethoxypropionate ethyl Part 20

Solvent: Propylene glycol monomethyl ether acetate 150 copies

The said component was mixed and stirred, and the photosensitive coloring composition coating liquid CB-1 for blue (B) was obtained.

4. Synthesis of Dispersion Resin A-3

4-1. Synthesis of Chain Transfer Agent A3

7.83 parts of dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Kagaku Kogyo Co., Ltd.] (Compound (33)), and an adsorption site, and also having a carbon-carbon double bond 4.55 parts of following compounds (m-6) were melt | dissolved in 28.90 parts of propylene glycol monomethyl ethers, and it heated at 70 degreeC under nitrogen stream. To this was added 0.04 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 3 hours. Furthermore, 0.04 part of V-65 was added and it was made to react at 70 degreeC under nitrogen stream for 3 hours. The 30% solution of the mercaptan compound (chain transfer agent A3) shown below was obtained by cooling to room temperature.

4-2. Synthesis of Dispersion Resin A-3

The mixed solution of 4.99 parts of the 30% solution of the chain transfer agent A3 obtained as mentioned above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether was heated at 90 degreeC under nitrogen stream. . 0.139 parts of 2,2'- azobisisobutyric acid dimethyl [V-601, Wako Pure Chemical Industries, Ltd. product], 5.36 parts of propylene glycol monomethyl ethers, and 9.40 parts of propylene glycol monomethyl ether acetates while stirring this mixed solution. The mixed solution was added dropwise over 2.5 hours. After 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'-azobisisobutyric acid and 4.00 parts of propylene glycol monomethyl ether acetate was added and reacted for another 2 hours. 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate were added to the reaction solution, followed by cooling to room temperature to obtain a solution of specific dispersion resin A-3 (weight average molecular weight 24000 in terms of polystyrene) (30 mass of specific dispersion resin). %, Propylene glycol monomethyl ether 21 mass%, propylene glycol monomethyl ether acetate) was obtained.

The acid value of this specific dispersion resin A-3 was 48 mgKOH / g. The structure of dispersion resin A-3 is shown below.

Production of color filter

Photosensitive coloring composition layer forming process

The obtained photosensitive coloring composition coating liquid CR-1 for red (R) was apply | coated to the black matrix formation surface side of the said black matrix substrate. Specifically, in the same manner as in the case of forming the photosensitive deep color composition layer, the interval between the slit and the black matrix substrate and the discharge amount were adjusted so that the layer thickness of the photosensitive colored composition layer after postbaking was about 2.1 μm, and the coating speed was 120 mm / sec. Applied.

Colored layer prebaking process, and colored layer exposure process

Subsequently, heating (prebaking process) was performed at 100 degreeC for 120 second using the hotplate, and it exposed at 90 mJ / cm <2> using the proximity type exposure machine (Model No. LE5565A Corporation Hitachi High Technology).

Moreover, the mask pattern and the exposure machine were set so that the overlap (exposure overlap amount) of an exposure pattern and a black matrix might be 5.5 micrometers.

Colored layer developing step, and colored layer baking step

Thereafter, the shower pressure was reduced with 1.0% developer (diluent containing 25 parts by mass of 1 part by mass of CDK-1 and 99 parts by mass of pure water) of potassium hydroxide developer CDK-1 (manufactured by Fujifilm Electronics Material Co., Ltd.). It set to 0.2 Mpa, and developed for 45 second and wash | cleaned with pure water.

Subsequently, it post-baked for 30 minutes in the clean oven of 220 degreeC, and formed the red pixel after heat processing.

Subsequently, the photosensitive coloring composition coating liquid CR-1 for red (R) in the said photosensitive coloring composition layer forming process, colored layer prebaking process, colored layer exposure process, colored layer developing process, and colored layer baking process is green. The green pixel was similarly formed except having changed into the photosensitive coloring composition coating liquid CG-1 for (G). Moreover, except then replacing the photosensitive coloring composition coating liquid CR-1 for red (R) with the photosensitive coloring composition coating liquid CB-1 for blue (B), blue pixels were similarly formed and the color filter was obtained.

SEM cross-sectional photographs of 10 pixels selected at random were taken, and the length in the width direction of the black matrix of the overlapping portion of the photosensitive coloring composition layer and the black matrix was measured. As a result, the arithmetic mean was 5.0 μm.

The SEM cross section photographed the cross section which was cut at right angles with respect to the long side direction near the center of the long side of the black matrix.

Moreover, the height of the "ridge | flop" of 100 colored patterns selected at random using the contact surface roughness meter P-10 (made by KLA Tencor Co., Ltd.) was 0.22 micrometers in an arithmetic mean. As shown in FIG. 8, the height measurement of the elevation was performed by moving the needle 12 in the width direction (A direction) of the black matrix 10 near the center of the lattice long side of the black matrix 10.

In addition, the height of the ridge formed by the coloring pattern of each color and the black matrix was calculated | required as distance in the normal line direction of the board | substrate between the part remote from the board | substrate surface of the overlap part among the surfaces of a coloring pattern, and flat surface parts other than the overlap part.

Manufacture of LCD

The ITO transparent electrode was also formed by sputtering on the R pixels, the G pixels, the B pixels, and the black matrix of the color filter obtained above. Separately, the glass substrate was prepared as a counter substrate, and the ITO transparent electrode was similarly formed by sputtering. And a columnar photospacer was formed in the part corresponding to the upper part of the partition on the said ITO transparent electrode, and the alignment film which consists of polyimide was further formed on it.

Thereafter, the sealing agent of the ultraviolet curable resin was applied by a dispenser method to a position corresponding to the black matrix outline formed around the colored pixel group of the color filter, the liquid crystal for TN mode was dropped and the counter substrate was placed in a vacuum state. Conjugation. The bonded substrate was subjected to UV irradiation and then heat treated to cure the sealing agent. In this way, a liquid crystal cell was obtained. The polarizing plate HLC2-2518 made from Sanlitz Co., Ltd. was stuck to both surfaces of this liquid crystal cell, Then, the backlight of a cold cathode tube was comprised and it arrange | positioned on the side used as the back surface of the liquid crystal cell provided with the said polarizing plate, and it was set as the liquid crystal display device.

Image quality evaluation of LCD

Various display images were visually observed by energizing a liquid crystal display device and evaluated according to the following evaluation criteria. The results are shown in Table 6 below.

Evaluation standard

(Circle): There is no stain, a display is clear and feels to be powerful.

(Triangle | delta): There is no stain, but I cannot feel force in a display.

X: There is a dirt, or it looks white and cannot see and enjoy it.

Examples 2 to 10 and 13 to 24

Example 1 WHEREIN: The photobaking composition coating liquid (it is described with a darkening composition in Table 5) using CK-1, the prebaking conditions in the black-matrix formation process, the image development conditions, and the coloring pattern formation process. A color filter was produced in the same manner as in Example 1 except that the exposure overlap amount was changed to the value shown in Table 5. A liquid crystal display device was produced in the same manner as in Example 1 using the color filter. Moreover, evaluation similar to Example 1 was performed. The results are shown in Table 6.

Example 11

The black matrix was formed by the transfer shown below, not by the coating, and the exposure machine was replaced with a mirror projection type exposure machine (model number MPA-8800, manufactured by Canon Corporation) corresponding to a larger substrate. A color filter was produced in the same manner as in Example 1 except for the above. The liquid crystal display device was produced using this color filter. Moreover, evaluation similar to Example 1 was performed. The results are shown in Table 6.

Formation of Black Matrix by Transfer

Fabrication of Photosensitive Transfer Material CK1

On the 75-micrometer-thick polyethylene terephthalate film support body (PET support body), the coating liquid for thermoplastic resin layers which consists of following formula H1 was apply | coated using a slit-shaped nozzle, it dried, and the thermoplastic resin layer was formed. Next, the coating liquid for intermediate | middle layers which consists of said prescription P1 was further apply | coated on a thermoplastic resin layer, and it dried, and formed the intermediate | middle layer (oxygen barrier film). On this intermediate | middle layer, the said photosensitive deepening composition coating liquid CK-1 was apply | coated, and it dried in 90 degree heat flow, and formed the photosensitive resin layer K1. Furthermore, the protective film (thickness 12 micrometer polypropylene film) was crimped | bonded to the surface of this photosensitive resin layer, and the photosensitive transfer material CK1 which integrated the support body, the thermoplastic resin layer, the intermediate | middle layer, and the photosensitive resin layer K1 was produced.

Coating liquid for thermoplastic resin layer: prescription H1

Methanol. Part 11.1

Propylene glycol monomethyl ether acetate... Part 6.36

Methyl ethyl ketone. Part 52.4

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C.)

                                                           … 6.80

Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, average molecular weight = 10,000, Tg ≒ 100 ° C.). Part 10.2

2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane

  (Shin-Nakamura Kagaku Kogyo Co., Ltd.)… Part 9.1

30% MEK (methyl ethyl ketone) solution of structure 1. 0.54part

The dry film thickness of the thermoplastic resin was 14.6 micrometers, the dry film thickness of the intermediate | middle layer was 1.6 micrometers, and the dry film thickness of the photosensitive resin layer K1 of the photosensitive transfer material CK1 obtained as mentioned above was 1.3 micrometers.

Next, the alkali free glass substrate (henceforth only called a "glass substrate") was wash | cleaned with the rotating brush which has nylon hair, spraying the glass detergent liquid adjusted to 25 degreeC by shower for 20 second, and also shower-washing with pure water. . After that, a silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsukagaku Kogyo Co., Ltd.) was sprayed for 20 seconds by showering to clean the pure water shower. did. This board | substrate was heated at 100 degreeC for 2 minutes using the board | substrate preheater.

The protective film is removed from the photosensitive transfer material CK1 obtained by the above to the obtained silane coupling process glass substrate, and the photosensitive resin layer K1 exposed after removal is overlapped so that the surface may contact the surface of a silane coupling process glass substrate, WO2006 Lamination was carried out using a large two-fold laminator as shown in Fig. 24 of -4225. The conditions (transfer conditions) of the laminate are shown in Table 2 below.

1. Facility Performance    Laminate speed 2.5m / min    Laminate tension 120 N / m 2. Substrate heating part    Substrate heating 120 ℃ 3. Disk part (roll of film to laminate)    width 1250 mm    Length 1000 m 4. Laminate part    Specification of Laminate Roll φ110 × 2650L (effective length 2500L) rubber roll    Laminate Pressure (Linear Pressure) 120 N / cm    Temperature of laminate roll Top Laminate Roll 95 ℃ Bottom Laminate Roll 120 ℃

Subsequently, the PET support was peeled off at the interface with the thermoplastic resin layer to remove the support. After peeling a branch body, it pattern-exposed at 100 mJ / cm <2> of exposure amounts by the mirror projection type exposure machine (MPA-8800, Canon Co., Ltd. product).

Next, a triethanolamine developer [30% containing triethanolamine, brand name: T-PD2 (manufactured by Fujifilm Co., Ltd.), diluted 12 times with pure water (solution of mixing 1 part of T-PD2 in the ratio of 11 parts of pure water)] Was shower-developed at 30 degreeC for 20 second by the flat nozzle pressure of 0.04 Mpa, and the thermoplastic resin layer and the intermediate | middle layer were removed. Subsequently, after spraying air on the upper surface of this glass substrate to remove the liquid, pure water was sprayed for 10 seconds by showering, pure shower cleaning, and air was sprayed to reduce liquid pool on the substrate.

Subsequently, showering pressure with 1.0% developer (diluent containing 1 part by mass of CDK-1 and 99 parts by mass of pure water, 28 ° C.) of potassium hydroxide developer CDK-1 (manufactured by Fujifilm Electronics Material Co., Ltd.) Was set to 0.10 MPa, and developed for 55 seconds to wash with pure water.

Subsequently, using a liquid obtained by diluting the washing agent [phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer; brand name: T-SD1 (manufactured by Fuji Film Co., Ltd.) 10-fold with pure water, It sprayed by shower at 0.02 Mpa of cone-shaped nozzle pressure for a second, and rubbed the pattern image formed by the rotating brush which has a soft nylon hair, the residue was removed, and the desired black matrix pattern was obtained.

Here, when the cross-sectional photograph was taken by SEM and the cross-sectional shape of the photosensitive deepening composition layer was observed, the taper length was about 1.5 micrometers. The measuring method of the said taper length was performed similarly to the measurement of the taper length in Example 1.

Subsequently, the post-baking process was carried out for 40 minutes in the clean oven at 220 degreeC, and the lattice-shaped black matrix whose opening of the colored pixel formation area | region is 90 micrometers x 200 micrometers, and the line width of a black matrix is about 25 micrometers was formed.

Example 12

A color filter was obtained in the same manner as in Example 11 except that the photosensitive deep color composition coating liquid CK-1 in Example 11 was changed to the following photosensitive deep color composition coating liquid CK-2, and a liquid crystal display device was used using the color filter. Made.

Preparation of Photosensitive Deep Color Composition Coating Liquid CK-2

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

Photosensitive deepening composition coating liquid CK-2 composition Pigment Dispersion K-2 30.0 Propylene Glycol Monomethyl Ether Acetate 7.3 Methyl ethyl ketone 34 Cyclohexanone 8.6 Binder 2 14.7 DPHA liquid 5.5 2,4-bis (trichloroethyl) -6- [4 '-(N, N-diethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine 0.22 Phenothiazine 0.006 Surfactant 1 00.058

In addition, the quantity shown in the said Table 3 is a mass part, The detail of each component is as showing below.

Pigment Dispersion K-2

13.1% of carbon black (Nipex35 made by Degussa)

Dispersant (compound 1 below) 0.65%

6.72% of polymer (benzyl methacrylate / methacrylic acid = random copolymer of 72/28 molar ratio, molecular weight 370,000)

Propylene glycol monomethyl ether acetate 79.53%

Binder 2

Polymer (benzyl methacrylate / methacrylic acid = 78/22 mole ratio random copolymer, molecular weight = 3.8 million). 27%

Propylene glycol monomethyl ether acetate... 73%

DPHA liquid

Mixture of 60 to 40 (mass ratio) of KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. and KAYARAD R-684 manufactured by Nippon Kayaku Co., Ltd.. 76%

Propylene glycol monomethyl ether acetate... 24%

Example 25

When applying the photosensitive deep color composition coating liquid CK-1 in the black matrix formation of Example 1, the space | interval between a slit and a glass substrate, and discharge amount are adjusted so that the black matrix film thickness after baking may be set to 1.5 micrometers, and the photosensitive deep color composition application is apply | coated. The color filter was manufactured like Example 1 except apply | coating solution CK-1 and changing each condition of the manufacturing process (black matrix formation process and colored pattern formation process) of a color filter like Table 5. Moreover, the liquid crystal display device was produced using this color filter.

Example 26

In forming the black matrix of Example 1, when the photosensitive deep color composition coating liquid CK-3 is changed to the photosensitive deep color composition coating liquid CK-3 and the photosensitive deep color composition coating liquid CK-3 is applied, the black matrix film thickness after baking becomes The interval between the slit and the glass substrate and the discharge amount were adjusted so as to be 1.8 µm, and the photosensitive deep color composition coating liquid CK-3 was applied, and the conditions of the color filter manufacturing process (black matrix forming step and colored pattern forming step) were shown. A color filter was produced in the same manner as in Example 1 except that the modification was carried out as in Example 5. Moreover, the liquid crystal display device was produced using this color filter.

Example 27

When applying the photosensitive deep color composition coating liquid CK-1 in the black matrix formation of Example 1, the space | interval between a slit and a glass substrate, and discharge amount are adjusted so that the black matrix film thickness after baking may be set to 1.0 micrometer, and the photosensitive deep color composition application is apply | coated. The color filter was manufactured like Example 1 except apply | coating solution CK-1 and changing each condition of the manufacturing process (black matrix formation process and colored pattern formation process) of a color filter like Table 5. Moreover, the liquid crystal display device was produced using this color filter.

Example 28

In forming the black matrix of Example 1, when the photosensitive deep color composition coating liquid CK-4 is changed to the photosensitive deep color composition coating liquid CK-4 and the photosensitive deep color composition coating liquid CK-4 is applied, the black matrix film thickness after baking becomes The interval between the slit and the glass substrate and the discharge amount were adjusted so as to be 0.7 μm, and the photosensitive deep color composition coating liquid CK-4 was applied, and the conditions of the color filter manufacturing process (black matrix forming step and colored pattern forming step) were shown. A color filter was produced in the same manner as in Example 1 except that the modification was carried out as in Example 5. Moreover, the liquid crystal display device was produced using this color filter.

Example 29

In Example 13, the color filter was manufactured like Example 13 except having changed the columnar spacer formation process as follows, and changing the developing conditions of the black matrix as Table 5. Moreover, the liquid crystal display device was produced using this color filter.

Spacer Forming Process

In preparation of the said photosensitive transfer material CK1, spacer formation which has a photosensitive resin composition layer with a dry layer thickness of 4.1 micrometers was carried out similarly to preparation of the photosensitive transfer material CK1 except having changed the photosensitive resin composition layer K1 into the prescription 1 shown in Table 4. A photosensitive transfer material was prepared. In addition, the unit in Table 4 is a mass part.

Coating liquid for photosensitive resin composition layer Prescription 1 1-methoxy-2-propyl acetate 26 Methyl ethyl ketone 28 Colloidal silica dispersion (colloidal silica: 30 parts, methyl isobutyl ketone: 70 parts, Nissan Kagaku Kogyo MIBKst) 14.1 Solsperth 20000 0.42 Carbon Black Dispersion 1 0 DPHA liquid (Dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2-propyl acetate: 24 parts) 9.1 Solution of resin P-1 20.5 Methacrylic acid / allyl methacrylate copolymer (molar ratio) = 20/80 (weight average molecular weight = 3.6 million) 0 Alkali-soluble resin (20) (50% of solid content) 0 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bis (ethoxycarbonylmethyl) amino) -3'-bromophenyl] -s-triazine 0.227 Hydroquinone monomethyl ether 0.0036 Surfactant 1 (Megapack F-780-F, Dai Nippon-Ink Kagaku Kogyo Co., Ltd.) 0.032 5% methanol solution of Victoria pure blue NAPS (product of Hodogaya Kagaku Kogyo KK) 2.05

Synthesis of Resin Represented by Compound Structure P-1

8.57 parts of 1-methoxy-2-propanol (made by Daicel Kagaku Kogyo Co., Ltd.) are previously added to a reaction container, and it heats up at 90 degreeC, 6.27 parts of isopropyl methacrylates, 5.15 parts of methacrylic acid, and azo polymerization The mixed solution which consists of 1 part of initiators (made by Wako Pure Chemical Industries Ltd., V-601) and 8.57 parts of 1-methoxy- 2-propanol was dripped over 2 hours in 90 degreeC reaction container under nitrogen gas atmosphere. After dropping, the mixture was reacted for 4 hours to obtain an acrylic resin solution.

Subsequently, after adding 0.025 part of hydroquinone monomethyl ether and 0.084 part of tetraethylammonium bromide to the said acrylic resin solution, 5.41 parts of glycidyl methacrylates were dripped over 2 hours. After dripping and reacting at 90 degreeC for 4 hours, blowing air, it prepared by adding solvent MMPGAC so that solid content concentration might be 45%, and obtained the resin solution represented by the following compound structure P-1 which has an unsaturated group.

In addition, the molecular weight (Mw) of resin represented by the said compound structure P-1 showed the weight average molecular weight, and measured using gel permeation chromatography (GPC) as a measuring method of the said molecular weight.

Preparation of alkali-soluble resin 20

Into the reaction vessel, a mixed solvent of 25 g of 1-methoxy-2-propanol and 25 g of 1-methoxy-2-propyl acetate is added in advance, and the temperature is raised to 90 ° C. to give 32.1 g of styrene, 36.5 g of methacrylic acid, and an azo polymerization initiator. (Made by Wako Pure Chemical Industries, V-601) A mixed solution of 6.73 g, 25 g of 1-methoxy-2-propanol, and 25 g of 1-methoxy-2-propyl acetate was placed in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere. It was dripped over time. After dropping, the mixture was reacted for 4 hours to obtain an acrylic resin solution.

Next, after adding 0.5 g of hydroquinone monomethyl ether and 0.015 g of tetraethylammonium bromide to the said acrylic resin solution, 31.3 g of glycidyl methacrylates were dripped over 2 hours. After dripping, it reacted at 90 degreeC for 4 hours, blowing air, and obtained the alkali-soluble resin solution. Solid content in this alkali-soluble resin 20 solution was 50%.

The cover film of the obtained photosensitive transfer material for spacer formation was peeled off, the surface of the exposed photosensitive resin composition layer was polymerized on a color filter substrate, and a linear pressure of 100 N / cm, using a large two-fold laminator as described in Fig. 24 of WO2006-4225, Bonding was carried out at a conveyance speed of 2 m / min under pressure and heating conditions of 130 ° C. Thereafter, the PET support was peeled off at the interface with the thermoplastic resin layer, and the photosensitive resin composition layer was transferred together with the thermoplastic resin layer and the intermediate layer.

Next, a mask (a quartz exposure mask having an image pattern) using a proximity exposure machine (manufactured by Hitachi High Technologies, Inc.) having an ultra-high pressure mercury lamp, and a color filter substrate arranged so that the mask and the thermoplastic resin layer face each other. In a state in which the surfaces of the photosensitive resin composition layer are in contact with the surface of the intermediate layer of the photosensitive resin composition layer, the distance between the mask surface and the surface of the photosensitive resin composition layer is 100 μm, and the exposure amount is 90 mJ / cm 2 at the thermoplastic resin layer side through the mask. It exposed.

Next, the triethanolamine-based developer (trade name: a solution diluted 12-fold with pure water) was shower-developed at 30 ° C for 50 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after spraying air on the upper surface of the glass substrate to remove the liquid, pure water was sprayed for 10 seconds by a shower, followed by pure shower cleaning, and air was sprayed to reduce the liquid level on the substrate.

Subsequently, it contains Na carbonate developer [0.38 mol / L sodium hydrogencarbonate, 0.47 mol / L sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, an antifoamer, and a stabilizer; FUJIFILM CO., LTD.] Was shower-developed at a cone nozzle pressure of 0.15 MPa for 50 seconds using a liquid diluted 10-fold with pure water, to obtain a pattern image of a spacer.

Subsequently, using a washing | cleaning agent [containing a phosphate, a silicate, a nonionic surfactant, an antifoamer, and a stabilizer; brand name: T-SD3 (liquid diluted 10-fold with Fuji Film Co., Ltd. product)] 20 at 33 degreeC The nozzle was sprayed at a cone nozzle pressure of 0.02 MPa for a second, and the surrounding residue on the formed pattern was removed to obtain a desired spacer pattern.

Next, the color filter substrate in which the spacer pattern was formed was heat-processed at 240 degreeC for 50 minutes (heat processing process), and the photo spacer was produced.

The obtained spacer pattern was cylindrical with a diameter of 24 µm and an average height of 3.6 µm. In addition, the average height of 20 spacers obtained was calculated | required by the arithmetic mean by measuring the highest position in the transparent electrode formation surface of ITO using the three-dimensional surface structure analysis microscope (maker: ZYGO Corporation, model: New View 5022).

Examples 30 and 31

In Example 1, the method of Example 1 was changed except having changed the columnar spacer formation process like Example 29, and changing the black matrix developing conditions as Table 5.

Example 32

In Example 1, the columnar spacer forming process was changed as in Example 29, the black matrix and the mask pattern of the pixel were changed so that the line width of the black matrix was 17 µm, and the overlapping amount was 4.5 µm. The same method as in Example 1 except that the conditions were changed as shown in the table.

Example 33

In Example 32, the color filter was manufactured like Example 32 except having changed the developing apparatus into the horizontal conveyance type. Moreover, the liquid crystal display device was produced using this color filter.

Example 34

In Example 32, the color filter was manufactured like Example 32 except having changed the developing apparatus into the vertical conveyance type. Moreover, the liquid crystal display device was produced using this color filter.

Comparative Example 1 to Comparative Example 6

In Example 1, it carried out similarly to Example 1 except having changed the prebaking conditions in a black-matrix formation process, the image development conditions, and the exposure overlap amount in a coloring pattern formation process into the value shown in Table 5. A filter was produced and a liquid crystal display device was produced in the same manner as in Example 1 using the color filter.

In Table 5, the unit of prebaking time and image development time in the "black matrix formation process" column is "second", and the unit of prebaking temperature and image development temperature is "degreeC". In addition, the unit of the exposure overlap amount in the "coloring pattern formation process" column is "micrometer".

Image quality evaluation was performed similarly to Example 1 about each liquid crystal display device produced by the said Example 2-Example 34, and Comparative Examples 1-6. The results are shown in Table 6.

In Comparative Examples 1 to 4, a colored pattern could not be formed on the substrate because a residue was generated after black matrix development, the line width of the black matrix became thick, or the black matrix was broken. In Comparative Example 5, since whitening such as a partial gap was generated between the black matrix and the pixels, it became a color filter unsuitable for subsequent evaluation and display device creation. Therefore, in Comparative Examples 1-5, the height of ridge cannot be calculated | required and the liquid crystal display device cannot be evaluated.

In Table 6, the unit of the thickness, the distance from the upper end to the lower end, the overlap, and the height of the ridge are all "µm".

As can be seen from Table 6, the heights of the elevations of the color filters of Examples 1 to 34 were suppressed, and it was found that the liquid crystal display device using these color filters was of high quality.

1 is a partial cross-sectional view of a black matrix substrate after development, in which the lower end portion almost coincides with the upper end portion.

2 is a partial cross-sectional view of the black matrix substrate after development in which reverse taper occurs.

3 is a partial cross-sectional view of the black matrix substrate after development where a forward taper is formed.

4 is a partial cross-sectional view of the black matrix substrate after the postbaking treatment.

5 is a partial cross-sectional view of a color filter substrate on which a colored layer is formed on a black matrix after postbaking treatment.

6 is a partial cross-sectional view of a color filter in which an overlap part is formed.

7 is a partial cross-sectional view of a color filter having raised portions in the overlap portion.

8 is a conceptual diagram of a measuring method for obtaining the height of a ridge.

Claims (17)

Forming the photosensitive deep color composition layer on the substrate using the photosensitive deep color composition, exposing the photosensitive deep color composition layer, and developing the photosensitive deep color composition layer after exposure, thereby forming the substrate from an upper end in the photosensitive deep color composition layer. Forming a black matrix pattern in which the distance in the width direction of the black matrix between the line extending in the normal direction and the lower end in the photosensitive deepening composition layer is located at -3.0 to +3.0 µm, A black matrix forming process comprising baking; And The photosensitive coloring composition layer is formed using the photosensitive coloring composition on the said board | substrate with which the said black matrix after baking is formed, the said photosensitive coloring composition layer is exposed, the said photosensitive coloring composition layer after exposure is developed, and the developed said Forming a coloring pattern by baking the photosensitive coloring composition layer, wherein the coloring pattern formation formed so that the length in the black-matrix width direction of the overlap part which the said coloring pattern after the said baking and said black matrix overlap may be 1.0 micrometer-12 micrometers. It has a process, The manufacturing method of the color filter characterized by the above-mentioned. The method of manufacturing a color filter according to claim 1, wherein the photosensitive deep color composition layer formed on the substrate has a thickness of 0.2 µm to 2.2 µm. The method for manufacturing a color filter according to claim 1, wherein in the development in the black matrix forming step, the development temperature is 20 ° C to 35 ° C, and the development time is 20 seconds to 120 seconds. The method of manufacturing a color filter according to claim 3, wherein the developing temperature is 20 ° C to 30 ° C, and the developing time is 30 seconds to 70 seconds. The method of claim 1, wherein the forming of the black matrix further comprises prebaking after the photosensitive deep color composition layer is formed and before the exposure. The method for manufacturing a color filter according to claim 5, wherein the prebaking temperature in the prebaking is 65 ° C to 120 ° C. The method of manufacturing a color filter according to claim 5, wherein the prebaking time in said prebaking is from 50 seconds to 300 seconds. The exposure in the said exposure pattern in the said coloring pattern formation process is performed through a mask pattern, The length in the width direction of the said black matrix of the overlapping part of an exposure pattern and the said black matrix is 3.0 micrometers- The manufacturing method of the color filter characterized by the above-mentioned. The method for manufacturing a color filter according to claim 8, wherein in the development in the coloring pattern forming step, the development temperature is 20 ° C to 35 ° C, and the development time is 20 seconds to 120 seconds. The said coloring pattern formation process of Claim 8 WHEREIN: The said length in the width direction of the said black matrix of the overlapping part of the said exposure pattern and the said black matrix is 2.0 micrometers-10 micrometers, The said developing temperature is 20 degreeC- It is 35 degreeC, The developing time is 20 second-120 second, The manufacturing method of the color filter characterized by the above-mentioned. The method of manufacturing a color filter according to claim 10, wherein the length is 3.0 µm to 8.0 µm, the development temperature is 20 ° C to 30 ° C, and the development time is 30 seconds to 70 seconds. The method of manufacturing a color filter according to claim 1, wherein a distance in a normal direction of the substrate between a portion farthest from the substrate surface of the overlap portion and a portion other than the overlap portion is 0.50 µm or less. The method of manufacturing a color filter according to claim 1, wherein the layer thickness of said photosensitive coloring composition layer is 0.5 µm to 3.0 µm. The color filter manufactured by the manufacturing method of the color filter of any one of Claims 1-13, Comprising: The overlap part which a black matrix and a coloring pattern overlap, The length in the said black matrix width direction of the said overlap part is It is 1.0 micrometer-12 micrometers, The color filter characterized by the above-mentioned. 15. The color filter according to claim 14, wherein the distance in the normal direction of the substrate between the portion farthest from the substrate surface of the overlap portion and the portion other than the overlap portion among the surfaces of the coloring pattern is 0.50 µm or less. The liquid crystal display device provided with the color filter of Claim 14. A liquid crystal display device comprising the color filter according to claim 15.

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