JP2007025358A - Color filter and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To permit production of a color filter, capable of satisfactorily performing dry etching, having satisfactory spectral characteristics and surface properties, superior rectangular properties of the pattern, and high adhesion with suppressed peeling. <P>SOLUTION: A colored layer is coated using a colorant-containing photocuring composition, containing colorants and photocuring compounds, wherein the density of the colorants in the total solid portion is ≥50 mass% and <100 mass%. The method includes a step for photocuring the applied colored layer due to exposure, before a photosensitive resin layer is formed on the colored layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter and a method for manufacturing the color filter, and more particularly to a color filter suitable for the configuration of a liquid crystal display element, a solid-state image sensor, and the like, and a method for manufacturing a color filter that forms a pattern by a dry etching method.

  As a method for producing a color filter used for a liquid crystal display element (LCD) or a solid-state image sensor (CCD, CMOS, etc.), a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then this coating film is subjected to pattern exposure and development. A colored filter is formed, and a color filter is obtained by repeating this operation for each color according to the desired number of hues. As such a pigment dispersion method, there is one in which an example using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, Patent Documents 1 to 4). reference).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

  In view of such a problem, a technique for using a dye instead of a pigment has been proposed (for example, see Patent Document 5). However, a curable composition using a dye has a problem that it is generally inferior to a pigment in various performances such as light resistance, heat resistance, solubility and coating uniformity. In addition, since a film thickness of 1.5 μm or less is required for use in the production of a color filter for a solid-state image sensor, a large amount of a dye must be added to the curable composition, and therefore, it is in close contact with the substrate. In addition, there is a problem that the pattern forming property is remarkably deteriorated such that the degree of curing is insufficient or the dye is removed from the exposed portion forming the filter.

  Regardless of pigments and dyes, the color filter using the photolithographic method has a disadvantage that the film thickness cannot be reduced because it is necessary to add a considerable amount of components other than the colorant, that is, a binder resin, a photopolymerizable compound, and an initiator. is there.

  In contrast to the color filter manufacturing method using the photolithography method, a dry etching method has been known for a long time as a method effective for forming a thinner and fine pattern. The dry etching method has been conventionally used as a method for forming a pattern on a dye-deposited thin film (see, for example, Patent Document 6), and the thin film formation has a film thickness of 1 while maintaining the same spectral characteristics as compared to a photolithography system. It is also possible to form a thin film of / 2 or less.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375 JP-A-55-146406

  However, recent color filters have a strong demand for thinning in order to improve image quality by reducing shading. In addition, in the above-described thin film formation by vapor deposition, contamination of the vapor deposition apparatus is unavoidable, and it becomes a heavy load for the production of a color filter, and since a pixel is mainly formed of pigments or dyes, a flattening film or an upper layer as a lower layer is formed. It was also one of the reasons why the yield did not increase.

  The present invention has been made in view of the above, and has a spectral characteristic and surface property that are excellent in pattern rectangularity, and has high adhesion between a substrate and an adjacent layer, and production of the color filter. It is an object of the present invention to provide a method for manufacturing a color filter with high cost performance using a dry etching method, and to achieve the object.

Specific means for solving the above problems are as follows.
<1> (1) A colorant-containing photocurable composition containing a colorant and a photocurable compound and having a concentration of the colorant in the total solid content of 50% by mass or more and less than 100% by mass on the substrate. Forming a colored layer on the substrate, (2) exposing and curing the colored layer formed on the substrate, and (3) providing a photosensitive resin layer on the cured colored layer for photosensitivity. Forming a photosensitive resin layer; (4) exposing at least the photosensitive resin layer imagewise and developing to form a pattern comprising the photosensitive resin layer; and (5) forming the pattern on the colored layer. And a step of performing a dry etching process using the pattern as a mask to form a colored pattern.

<2> The method for producing a color filter according to <1>, wherein the concentration is 60% by mass or more and 95% by mass or less.
<3> The method for producing a color filter according to <1>, wherein the concentration is 65% by mass or more and 90% by mass or less.
<4> The <1> to <3, wherein the photocurable compound is a radical polymerizable monomer having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure. The method for producing a color filter according to any one of the above.
<5> The method for producing a color filter according to any one of <1> to <4>, wherein the colorant-containing photocurable composition further includes a photopolymerization initiator and is configured in a negative shape. It is.
<6> The method for producing a color filter according to any one of <1> to <4>, wherein the colorant-containing photocurable composition includes an o-naphthoquinonediazide compound and is configured in a positive type. It is.
<7> The method for producing a color filter according to any one of <1> to <6>, wherein the colored layer has a thickness of 0.005 to 0.9 μm.
<8> A color filter produced by the method for producing a color filter according to any one of <1> to <7>.

  According to the present invention, the spectral characteristics and surface properties are good and the pattern rectangularity is excellent, and the color filter having high adhesion between the substrate and the adjacent layer is suitable for the production of the color filter, and dry etching. It is possible to provide a method of manufacturing a color filter with high cost performance using the method.

  Hereinafter, the manufacturing method of the color filter of the present invention will be described in detail, and the color filter of the present invention will be described in detail through the description.

  The method for producing a color filter of the present invention is formed by providing the steps shown in the following (1) to (5), specifically, patterning a colored layer that is colored and cured by light by a dry etching method. And may include other steps as necessary.

(1) A colorant-containing photocurable composition containing a colorant and a photocurable compound and having a concentration of the colorant in the total solid content of 50% by mass or more and less than 100% by mass is provided on a substrate. A step of forming a colored layer (for example, by applying and drying) (hereinafter sometimes referred to as a “colored layer forming step”).
(2) A step of exposing and curing the colored layer formed on the substrate (hereinafter sometimes referred to as “photocuring step”).
(3) A step of providing a photosensitive resin layer on the cured colored layer (for example, applying and drying) to form a photosensitive resin layer (hereinafter, sometimes referred to as “resist formation step”).
(4) A step of exposing at least the photosensitive resin layer imagewise and developing to form a pattern composed of the photosensitive resin layer (hereinafter sometimes referred to as a “mask forming step”).
(5) A process of forming a colored pattern by subjecting the colored layer to a dry etching process using the pattern as a mask (hereinafter sometimes referred to as an “etching process”).

  The color filter produced by the method for producing a color filter of the present invention may be composed of a single color or may be composed of two or more colors. When it consists of multiple colors, it consists of multiple colors by repeating the above colored layer forming step, photocuring step, resist forming step, mask forming step, etching step, and other steps as needed. A color pattern can be produced. At this time, since the mask for the dry etching process is unnecessary when forming the pattern of the color to be finally formed, it is not necessary to perform the steps (3) and (4) after photocuring. A multicolored color filter can be formed by removing the excess colorant-containing photocurable composition present on the pattern and performing planarization. Hereinafter, each step will be described in detail.

-Colored layer formation process-
In the colored layer forming step, the colored layer-containing photocurable composition is provided on the substrate to form the colored layer. The colorant-containing photocurable composition comprises a colorant having a concentration in the total solid content of 50% by mass or more and less than 100% by mass and a photocurable compound. To do.

The colored layer can be formed by, for example, a method of applying and drying. In the case of coating, the colorant-containing photocurable composition is formed on the substrate by a coating method such as spin coating, slit coating, cast coating, roll coating, or the like, directly or through another layer, and then dried. it can.
The thickness of the colored layer is preferably 0.005 to 0.9 μm, more preferably 0.01 to 0.65 μm, and particularly preferably 0.02 to 0.6 μm.

Examples of the substrate include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to them, and photoelectric conversion element substrates used for imaging elements and the like. (For example, silicon substrate), complementary metal oxide semiconductor (CMOS), and the like. These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer may be provided on these substrates for the purpose of improving adhesion with a provided layer (for example, a colored layer), preventing diffusion of a substance, or flattening the surface.

-Photocuring process-
In the photocuring step, the colored layer formed on the substrate is photocured by exposure using light or radiation. This step may be performed simultaneously with drying after coating when the colored layer is formed in the colored layer forming step by coating, or may be separately provided for photocuring after coating and drying. It may be.

  As light or radiation used in this step, a conventionally known light source can be selected and used. Specifically, ultra high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser lamps in the visible or ultraviolet range, fluorescent lamps, tungsten lamps, and sunlight Etc. can be used. Among these, a mercury lamp is preferable, and a high-pressure mercury lamp including g-line, h-line, and i-line is particularly preferable.

About exposure conditions, such as irradiation time and irradiation amount, it can select suitably so that desired curability may be acquired with respect to a colorant containing photocurable composition, As light quantity required for specific hardening, it is set to 0. A range of 001 to 2000 mJ / cm ² is preferable, and a range of 0.5 to 850 J / cm ² is more preferable.

-Resist formation process-
In the resist forming step, a positive or negative photosensitive resin composition is provided on the colored layer cured in the photocuring step to form a photosensitive resin layer. This photosensitive resin layer is a layer constituting a mask pattern formed in a mask forming process described later.

  Formation of the photosensitive resin layer can be performed by, for example, a method of coating and drying. In the case of coating, it can be suitably carried out using a coating method such as spin coating, slit coating, cast coating, roll coating or the like directly on the colored layer or via another layer.

  The positive photosensitive resin composition is sensitive to radiation such as ultraviolet rays such as g rays, h rays and i rays, far ultraviolet rays including excimer lasers, electron rays, ion beams and X rays. A positive photosensitive resin composition suitable as a mold photoresist can be used. In this case, g-line or i-line is preferable as light or radiation, and exposure with i-line is particularly preferable.

  Specifically, as the positive photosensitive resin composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. The positive type photosensitive resin composition containing a quinonediazide compound and an alkali-soluble resin is decomposed from a quinonediazide group by irradiation with light having a wavelength of 500 nm or less to generate a carboxyl group, and from an alkali-insoluble state to an alkali-soluble state. It can be used as a positive-type photoresist utilizing change. Note that this positive type photoresist is remarkably excellent in resolving power, and is therefore used in the manufacture of integrated circuits such as ICs and LSIs. A preferred example of the quinonediazide compound is a naphthoquinonediazide compound.

  In recent years, with respect to integrated circuits, the width of wiring has become finer as the degree of integration increases, and for this reason, dry etching has become the mainstream in place of conventional wet etching. In this dry etching, the shape of the resist is directly reflected in the shape of the layer to be etched. Therefore, if the shape of the resist is poor, etching is performed up to a portion that does not require etching, which may cause defective integrated circuits and poor yield. For this reason, a resist having a good profile with little development residue (scum) or the like is required more than ever. Further, in dry etching, the temperature of the substrate rises, and the resist pattern may be thermally deformed to reduce the dimensional accuracy. For this reason, the heat resistance of a resist is requested | required more than before. From this point of view, many positive photoresists satisfying various performances such as profile, scum, resolution, and heat resistance are commercially available. As a suitable one, for example, FUJIFILM Electronics Materials Co., Ltd. FH-6000 series, such as FH-6400L, FH-6800L, FHi-3000 series, such as FHi-3200, FHi-3950, etc., FHi-600 series, such as FHi-644, FHi, etc. -645, Fi-SP series made by the same company, for example, Fi-SP2 and the like. However, the present invention is not limited to this, and it can be used as a positive-type photosensitive resin composition regardless of whether it is commercially available as long as it has a mask shape preferable for pattern formation.

  Examples of the negative photosensitive resin composition include negative sensitive to ultraviolet rays such as g rays, h rays and i rays, far ultraviolet rays, X rays, electron rays, molecular rays, gamma rays, synchrotron radiation and the like. Type photoresist. Furthermore, a negative photoresist which is excellent in resolving power and sensitivity and in which minute defects due to residual development is not substantially generated is preferable.

For example, a negative photoresist is applied on the colored layer to a thickness of, for example, 0.5 to 3 μm by the above-described application method, and then heated and dried, and then cured into a desired pattern by irradiating the desired pattern with ultraviolet rays through an exposure mask. If necessary, after the exposure, a heating step (PEB) is further performed, followed by development to obtain a negative image obtained by processing a photoresist (photosensitive resin layer) into a pattern. It can be used as a mask for exposure in the process.
Typical examples include semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photo application processes. Moreover, it can also be applied to a lithographic printing plate by utilizing the difference in affinity between the image and the support substrate for ink. With higher integration of semiconductor substrate processing, higher resolution of the photoresist is required.

  The negative photosensitive resin layer is preferably a layer containing a photopolymerization initiator and a polymerizable compound having an ethylenically unsaturated bond. A negative photosensitive resin composition that can be used to form such a photosensitive resin layer is shown below. For example, Japanese Patent Publication No. 54-23574 discloses a technique for photocuring a novolak resin in combination with a photoacid generator composed of an organic halide, and West German Published Patent No. 2057473 discloses a photoacid generator composed of a diazo compound. A phenolic resin such as novolak can be applied as a binder between the photocurable composition comprising methylolated melamine and the like, and JP-A-60-263143 discloses a photoacid generator and an acid such as melamine resin. A composition comprising a curable aminoblast resin and a general novolak resin is disclosed, and it is said that a negative image capable of aqueous development and having high thermal stability can be obtained. JP-A-62-164045 describes that an organic halide having light absorption in the far ultraviolet region can be advantageously used as a photoacid generator, and similarly, JP-A-2-52348 discloses. Describes that an organic halide having a pKa value in a specific region is advantageous as a similar photoacid generator. Furthermore, JP-A-2-154266 describes that oxime sulfonic acid esters are effective as a photoacid generator for a photocurable composition. As another example, in JP-A-2-146444, a composition comprising a photoacid generator having a specific trichlorotriazine group and a novolak resin containing 30% or more of m-cresol in alkoxylated melamine, It is described that it is useful for high energy beam exposure. Further, European Patent No. 396460A also describes the use of a novolak resin having a high degree of branching in a similar composition.

  There are commercially available negative photosensitive resin compositions such as those described above, such as the SC series (for example, SC-60, SC-450, etc.) manufactured by FUJIFILM Electronics Materials Co., Ltd. HR series (for example, HR-100, HR-200, etc.) made by the company, HNR series (for example, HNR-80, HNR-120, etc.) made by the same company, etc. are mentioned. However, the present invention is not limited thereto, and any mask having a shape preferable for pattern formation can be used regardless of whether it is commercially available.

  The layer thickness of the photosensitive resin layer is preferably 0.01 to 3 μm, more preferably 0.1 to 2.5 μm, and still more preferably 0.15 to 2 μm.

-Mask formation process-
In the mask forming step, at least the photosensitive resin layer provided in the resist forming step is exposed and developed imagewise, and a pattern (etching mask) made of the photosensitive resin layer is formed on the colored layer by photolithography. .

  The exposure can be suitably performed by selecting a light source that emits light having a wavelength corresponding to at least the photosensitive wavelength of the photosensitive resin layer. The g-line, h-line, i-line, etc., particularly preferably the i-line is preferably a predetermined mask pattern. It can be performed in a pattern by irradiating via, for example.

  In the development, the photosensitive resin layer after the exposure is alkali-developed with a developer. By the alkali development in this step, the non-cured portion of the positive or negative photosensitive resin composition is developed and removed in accordance with the latent image formed on the photosensitive resin layer by the exposure, and is made of a cured photoresist. A pattern is formed. This pattern functions as a mask when forming a pattern on the colored layer in an etching process described later.

  Development can be performed using a developer, and any developer can be used as long as it can dissolve the exposed portion of the positive photoresist or the unexposed portion of the negative photoresist without adversely affecting the colored layer. Can also be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The alkaline aqueous solution may be an alkaline developer, and those generally marketed have stable performance and good reproducible results. As commercially available products, for example, FHD-5 and CD-2000 manufactured by FUJIFILM Electronics Materials are suitable, but are not limited thereto.

  Processing conditions such as development temperature and development time during development can be appropriately selected depending on the configuration of the image recording material, the type of developer used, and the like.

-Etching process-
In the etching step, the colored layer exposed by alkali development in the mask forming step is subjected to a dry etching process, and the colored layer is processed into a pattern. The pattern formed in this step constitutes a color filter or a colored pixel of the color filter.

  Representative examples of the dry etching method include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102. As described in the above publications, there is a method in which a coloring agent is vapor-deposited, a mask resist is applied, and etching is performed after patterning.

In the dry etching of this step, it is possible to perform anisotropic etching using CF-based gas such as oxygen and CF ₄ , CO, CO ₂ gas, etc., and the colored layer is etched according to the pattern of the pattern mask, and rectangular A color pattern (color filter) having excellent properties can be formed.

  After the etching step, the pattern mask, that is, the photosensitive resin layer (photoresist) provided on the colored layer in a pattern shape can be removed using a dedicated stripping solution or solvent. Such removal may be performed after all of the above five steps are completed, and after the removal, the second and subsequent color patterns can be produced by repeating the same steps. When forming the last color pattern, after photocuring, the excess photocurable composition remaining on the existing color pattern is removed and flattened to produce a pattern of all colors. You may do it.

  In the method for producing a color filter of the present invention, the color filter or the colored layer constituting the colored pixel may be photocured, and it is not necessary to develop by alkali development at all, and is equivalent to a color filter produced by a photolithography method. Thin film can be realized as much as the alkali-soluble binder can be reduced as much as possible while having the spectral characteristics of the degree. Usually, in order to realize a thin film, it is necessary to increase the solid content concentration with respect to a coating film produced by a photolithography method. On the other hand, in order to obtain desired spectral characteristics, it is necessary to improve the concentration of the colorant. For this reason, if a thin film is formed while maintaining the desired spectral characteristics by the photolithography method, the solid content other than the colorant will be lowered, resulting in poor curing and loss of the pattern due to alkali development. (Flow in development and rinsing process). For this reason, there is a limit to the colorant concentration in thinning the film by the photolithographic method. In particular, when the colorant concentration is 65% by mass or more, pattern formation is almost impossible.

  In contrast, the color filter of the present invention cures a colored layer containing a colorant with light and forms a colored pattern using dry etching. Therefore, an alkali-soluble binder that is an essential component for the photolithography method. Need not be included in the colored layer other than as an additive for ensuring the coating surface condition. For this reason, it can be comprised with a coloring agent and a photocurable compound, and a photoinitiator as needed, and the density | concentration of a coloring agent can be made into the high density | concentration of 50 mass% or more, especially 65 mass% or more.

  In the present invention, if the colorant concentration is 50% by mass or more, the thickness of the colored layer, that is, the color filter can be reduced to the above-described range. For example, the colorant concentration can be further set to 70% by mass or more. That is, it is possible to form a film that is thinner than the limit of the photolithographic method with almost no change in spectral characteristics. In addition, by providing adhesion to components other than the colorant, adhesion performance that could not be obtained by the vapor deposition method can be realized even in a system with a high colorant concentration.

  The concentration of the colorant is preferably 100% by mass as in the vapor deposition method, and the film thickness is also the thinnest in the vapor deposition method. However, in the vapor deposition method, there is a problem of (1) equipment contamination. (2) Adhesion between the substrate and the adjacent layer may be insufficient.

Next, the coloring agent containing photocurable composition used for the manufacturing method of the color filter of this invention is demonstrated.
The colorant-containing photocurable composition according to the present invention comprises at least a colorant and a photocurable compound so that the concentration of the colorant in the total solid content is 50% by mass or more and less than 100% by mass. It is configured. Moreover, Preferably, it contains a photoinitiator and may contain the other additive as needed.

-Colorant-
The colorant-containing photocurable composition according to the present invention contains at least one colorant. This colorant includes known pigments and dyes, and can be appropriately selected according to the purpose and the case.

<Pigment>
As the pigment, conventionally known various inorganic pigments or organic pigments can be used. In addition, it is preferable to use pigments that are as fine as possible, whether inorganic or organic. In consideration of handling suitability, the average particle diameter of the pigment particles is preferably 0.001 to 0.1 μm, 005 to 0.05 μm is more preferable.
Further, the pigment particularly preferably contains 75% by mass or more of pigment particles having a particle size distribution within a range of 0.01 ± 0.005 μm with respect to the total mass of the pigment. Such a particle size distribution is particularly preferably obtained by dispersing the pigment by a dispersion method described later.

  Examples of the inorganic pigment include metal compounds represented by metal oxides and metal complex salts, and specifically, aluminum, iron, cobalt, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like. Mention may be made of metal oxides and complex oxides of the above metals.

As the organic pigment,
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, 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;
Etc.

Among the above, preferable organic pigments are listed below. However, the present invention is not limited to these.
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, 32;
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

  The organic pigments may be used alone or in combination of a plurality of types in order to increase color purity. Specific examples include red pigments such as anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, and quinophthalone pigments. A combination with a yellow pigment or a perylene red pigment can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83 or C.I. I. A combination with Pigment Yellow 139 is preferred. The mass ratio (R: Y) between the red pigment (R) and the yellow pigment (Y) is preferably 100: 5 to 100: 50, more preferably 100: 10 to 100: 30. When the mass ratio is within the above range, the light transmittance can be suppressed to improve the color purity, and further, the main wavelength can be prevented from being shifted from the NTSC target hue due to the short wavelength. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or a combination thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio (G: Y) between the green pigment (G) and the yellow pigment (Y) is preferably 100: 5 to 100: 150, more preferably 100: 30 to 100: 120. When this mass ratio is within the above range, the light transmittance of 400 to 450 nm can be suppressed, the color purity can be improved, and further, the main wavelength becomes longer than that of the NTSC target hue. can do.

  As the blue pigment, a phthalocyanine pigment alone or a combination of this with a dioxazine purple pigment can be used. Examples of the combination include C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio (B: V) between the blue pigment (B) and the purple pigment (V) is preferably 100: 0 to 100: 30, and more preferably 100: 0 to 100: 10.

  Furthermore, by using a powdery processed pigment in which the pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, etc., a composition having good dispersibility and dispersion stability can be obtained. Can be prepared.

  In the colorant-containing photocurable composition of the present invention, it is preferable to use a pigment having finely divided pigment particles and a sharp particle size distribution. Specifically, it is preferable to use a pigment composed of pigment particles having an average particle size of about 0.01 μm and a particle size of 75% by mass or more in the range of 0.01 ± 0.005 μm. In order to adjust the particle size distribution of the pigment to the above range, the pigment dispersion method is particularly important, and the pigment dispersion method will be described later.

  In the present invention, processed pigments previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be suitably used. In the present invention, the processed pigment treated with the various resins is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed.

<dye>
The dye can be used without any particular limitation, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828.

  From the viewpoint of chemical structure, azo compounds such as pyrazole azo, anilino azo, pyrazolo triazole azo, pyridone azo, triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine , Xanthene, phthalocyanine, benzopyran, indigo, anthrapyridone and the like can be used, preferably pyrazole azo, anilinoazo, pyrazolotriazole azo, pyridone azo, anthraquinone, anthrapyridone It is a dye.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used from the viewpoint of completely removing a binder and / or dye described later by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
Hereinafter, the acid dye and its derivative will be described in detail.

-Acid dyes and their derivatives-
The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the present invention is not limited to these. For example,
Acid alizarin violet N;
Acid black 1, 2, 24, 48;
Acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
Acid chroma violet K;
Acid Fuchsin;
Acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
Acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

Acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
Acid violet 6B, 7, 9, 17, 19;
Acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes, Acid black 24;
Acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
Acid orange 8, 51, 56, 74, 63;
Acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
Acid violet 7;
Acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Acid green 25;
Dyes such as these and derivatives of these dyes are preferred.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Solvent Orange 45; Rhodamine B, Rhodamine 110, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino] -2,7-naphthyl, etc. These acid dyes and derivatives of these dyes can also be suitably used.

  As the derivative of the acid dye, an inorganic salt of an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, etc. can be used, and a curable composition solution Is not particularly limited as long as it can be dissolved, but it requires solubility in organic solvents and developer, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. It is selected considering all of the performance.

The method for forming the “salt of an acid dye and a nitrogen-containing compound” may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent), and improving heat resistance and light resistance.
Next, a nitrogen-containing compound that forms a salt with an acidic dye and a nitrogen-containing compound that forms an amide bond with an acidic dye will be described.

  The nitrogen-containing compound is a salt or amide compound in an organic solvent or developer, salt-forming property, dye absorbance / color value, interaction with other components in the curable composition, heat resistance as a colorant. Selected in consideration of all of light and light resistance. When selecting only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible. Among them, a molecular weight of 300 or less is preferable, a molecular weight of 280 or less is more preferable, and a molecular weight of 250 or less. Are particularly preferred.

The molar ratio (hereinafter referred to as n) of the nitrogen-containing compound / acid dye in the “salt of acid dye and nitrogen-containing compound” is a value that determines the molar ratio of the acid dye molecule and the amine compound that is a counter ion. And can be freely selected according to the salt forming conditions of the acid dye-amine compound.
Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting only from the viewpoint of absorbance, n preferably takes a numerical value between 0 <n ≦ 4.5, more preferably a numerical value between 0 <n ≦ 4, and 0 <n ≦ It is particularly preferred to take a numerical value between 3.5.

  Since the acidic dye is an acidic dye by introducing an acidic group in structure, it can be made a non-acidic dye by changing the substituent. In addition, the acid dye may suitably act during alkali development, but on the other hand, it may be over-developed, and a non-acid dye may be preferably used.

  The concentration of the colorant in the colored layer is preferably 50% by mass or more and less than 100% by mass, more preferably 60% by mass or more and 95% by mass or less, and particularly preferably 65% by mass or more and 90% by mass or less with respect to the total solid content. preferable. When the concentration of the colorant is within the above range, desired spectral characteristics can be obtained, and it is effective for forming an image with good gray balance (including a color filter), and it is also preferable from the viewpoint of curability.

-Photocurable compound-
The colored layer (or the colorant-containing photocurable composition) contains at least one photocurable compound. Examples of photocurable compounds include radically polymerizable monomers such as single-capacity and polyfunctional acrylates, radically polymerized oligomers such as polyester acrylates, urethane acrylates, and epoxy acrylates, as well as radically polymerized polymers and epoxy as cationically polymerized compounds. In general, oxetane and the like are mentioned.

  The radical polymerizable monomer is preferably a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure. By containing this radical polymerizable monomer together with a photopolymerization initiator, which will be described later, the colorant-containing photocurable composition can be configured to have a negative photocurability.

  Examples of radically polymerizable monomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and (meth) acrylate after addition of ethylene oxide or propylene oxide, Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52- Examples include polyester acrylates described in each publication of No. 30490, polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers.

  As content in the coloring agent containing photocurable composition in the case of using a radically polymerizable monomer, 0.1-70 mass is preferable with respect to the total solid (mass) of this composition, and 1.0- 60 mass% is still more preferable, and 2.0-50 mass% is especially preferable.

  Moreover, as total content in the coloring agent containing photocurable composition of a photocurable compound, although it changes also with a raw material, 0.1-90 mass% is with respect to the total solid (mass) of this composition. Preferably, 0.2-80 mass% is more preferable, and 1-70 mass% is especially preferable.

-Photopolymerization initiator-
In addition to the above, the colorant-containing photocurable composition according to the present invention preferably contains at least one photopolymerization initiator together with the photocurable compound (particularly a radical polymerizable monomer). By containing this photopolymerization initiator together with the above-described photocurable compound (particularly, radically polymerizable monomer), the photocolorant-containing curable composition can be suitably configured as a negative type.

  The photopolymerization initiator is not particularly limited as long as it can polymerize a photocurable compound (particularly a radical polymerizable monomer), but is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. Is preferred.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole-based compound and a halomethyl-s-triazine-based compound, a 3-aryl-substituted coumarin compound, a lophine dimer, and a benzophenone compound. Acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of the active halogen compound which is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloro Methyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p- Methoxystyryl) -1,3,4-oxadiazole, and the like.

  Examples of the active halogen compound that is the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in Japanese Patent Publication No. 59-1281 and 2- (naphtho) described in JP-A-53-133428. -1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specifically, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1 , 3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)- , 6-Bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (for example, T-OMS, T-BMP, TR, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Ciba Specialty Chemicals) Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4'-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1, 2-octanedione, 2 Benzyl-2-dimethylamino-4-morpholinobutyrophenone Ciro acetophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, Also useful are 4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like.

  A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators. Specific examples include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxy Xanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) Phenyl-p-methylstyryl ketone, Examples include zophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, and tinuvin 1130, 400. It is done.

In addition to the photopolymerization initiator, other known initiators can also be used.
Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Patent Nos. 3,046,127 and 2,951,758, and triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367. Combinations, benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516, and the like can be mentioned.

  The total amount of the photopolymerization initiator (and the known initiator) is preferably 0.01 to 50% by mass with respect to the solid content (mass) of the photocurable compound (particularly the radical polymerizable monomer), 1-30 mass% is more preferable, and 1-20 mass% is especially preferable. When the total amount used is within the above range, good polymerization reactivity and film strength can be ensured.

-Other various additives-
The colored layer and the colorant-containing photocurable composition that constitutes the colored layer, in addition to the above-described components, other various additives as necessary, for example, a binder, a cross-linkage, as long as the effects of the present invention are not impaired. Various additives such as an agent, a curing agent, a curing catalyst, a solvent, a filler, a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and a dispersant can be added. .

<binder>
The colored layer (or the colorant-containing photocurable composition) can be suitably configured using at least one binder. In the present invention, if the photocurable compound can form a film at the time of coating, it is not necessary to contain it, and it can be used supplementarily for the purpose of improving the coating film surface condition. In addition, since the photolithography process is not required in the method for producing a color filter of the present invention, the binder is not particularly limited, and the viewpoints of heat resistance, developability, availability, etc. regardless of whether it is water-soluble or alkali-soluble. Is preferably selected from. Moreover, when adding a binder at the time of preparation of a pigment dispersion, it is preferable to have organic solvent solubility, although alkali solubility is not required.

  The binder is preferably a linear organic polymer that is soluble in an organic solvent. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to the above, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.

  Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  In addition to the above, the hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid site, phosphate ester site, quaternary ammonium salt site, ethyleneoxy chain site, propyleneoxy chain site, sulfonic acid and its salt site, morpholinoethyl. A monomer containing a group or the like is also useful.

  In order to improve the crosslinking efficiency, the polymer may have a polymerizable group in the side chain, and a polymer containing a polymerizable group such as an allyl group, a (meth) acryl group, or an allyloxyalkyl group in the side chain. Useful. Examples of the “polymer containing a polymerizable group in the side chain” include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. . From the viewpoint of increasing the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin, and the like are also useful.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

  As the acrylic resin, a copolymer comprising monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, for example, benzyl methacrylate / methacrylic acid, Each copolymer such as benzyl methacrylate / benzylmethacrylamide, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

  By dispersing the colorant in these binders at a high concentration, it is possible to impart adhesion to the lower layer and the like, which also contributes to the coated surface shape during spin coating and slit coating.

As the binder, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 5000 to 5 × 10. The polymer of ⁴ is particularly preferred.

  The content of the binder in the colored layer or the colorant-containing photocurable composition is preferably 0.1 to 50% by mass with respect to the total solid content (mass), and from the viewpoint of thinning the colored layer. Since it is preferable that the amount is as small as possible, 0.2 to 40% by mass is more preferable, and 1 to 35% by mass is particularly preferable.

<Crosslinking agent>
In the present invention, it is also possible to obtain a more highly cured film by additionally using a crosslinking agent.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least one substitution selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A phenol compound substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with a group, naphthol A compound or a hydroxyanthracene compound. Of these, polyfunctional epoxy resins are particularly preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. Divalent glycidyl group-containing low molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, and the like; Trivalent glycidyl group-containing low molecular weight compounds typified by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc .; similarly, pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether and the like; similarly, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether; And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as (b) -containing (methylol group, alkoxymethyl group or acyloxymethyl group-containing) compound.

  The methylol group-containing compound in (b) can be obtained by heating the alkoxymethyl group-containing compound in (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound in (b) can be obtained by mixing and stirring the methylol group-containing compound in (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound in (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine, or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds in (b) may be used alone or in combination.

  The compound in the above (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is a compound in the above (b). As in the case of, the intermixing with the overcoated photoresist is suppressed and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the compound in (c) is at least 2 per molecule, and from the viewpoint of curing and storage stability, A compound in which all of the 2- and 4-positions are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound serving as the skeleton are also preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound in (c) is a compound in which the phenolic OH group has a hydrogen atom at the 2nd or 4th position, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide, etc. Obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound in (c) can be obtained by heating the methylol group-containing compound in (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like in alcohol.
The acyloxymethyl group-containing compound in the above (c) can be obtained by reacting the methylol group-containing compound in the above (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in (c) include phenol compounds, naphthol compounds, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol A and other bisphenols; 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the above (c) include, as a phenol compound or a naphthol compound, for example, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, or trimethylol. Compounds obtained by methoxymethylating one or two methylol groups of -3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol , Tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl -4,4'-bishydroxybiphenyl, hexamethylol body of TrisP-PA, hexamethoxymethyl body of TrisP-PA, a compound obtained by methoxymethylating 1 to 5 methylol groups of the hexamethylol body of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include a part of the methylol group of the methylol group-containing compound, or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds in (c) may be used singly or in combination of two or more.

  The total content of the crosslinking agent in the colored layer or the colorant-containing photocurable composition varies depending on the material, but is preferably 1 to 70% by mass with respect to the total solid content (mass) of the layer or composition. 5 to 50 mass% is more preferable, and 7 to 30 mass% is particularly preferable.

<Thermal polymerization inhibitor>
A thermal polymerization inhibitor may be further added to the colorant-containing photocurable composition according to the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

<Curing agent>
The colored layer (or the colorant-containing photocurable composition) can be suitably configured using at least one curing agent. When using an epoxy resin as the photocurable compound, it is preferable to add a curing agent. In this case, it reacts with an epoxy group, undergoes a polymerization reaction, and is cured by improving the crosslinking density.

  There are many types of curing agents for epoxy resins, and the properties, pot life of the resin and curing agent mixture, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used, An appropriate curing agent must be selected according to the purpose of use, usage conditions, working conditions, and the like of the curing agent. The curing agent is explained in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of curing agents are given below.

  As those that act catalytically, tertiary amines, boron trifluoride-amine complexes react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc., and room temperature curing Examples thereof include diethylenetriamine and polyamide resin, examples of medium-temperature curing include diethylaminopropylamine and tris (dimethylaminomethyl) phenol, and examples of high-temperature curing include phthalic anhydride and metaphenylenediamine. From the viewpoint of chemical structure, in the case of amines, diethylenetriamine is used as an aliphatic polyamine, metaphenylenediamine is used as an aromatic polyamine, tris (dimethylaminomethyl) phenol is used as an acid anhydride, and anhydride is used as an acid anhydride. Phthalic acid, polyamide resin, polysulfide resin, boron trifluoride-monoethylamine complex, and synthetic resin initial condensate include phenol resin, other dicyandiamide, and the like.

  In the case of adding a curing agent, the amount is preferably as small as possible from the viewpoint of reducing the thickness of the colored layer. Specifically, it is preferably 35% by mass or less, more preferably 30%, based on the solid content (mass) of the colored layer. It is at most mass%, more preferably at most 25 mass%.

<Curing catalyst>
The colored layer (or the colorant-containing photocurable composition) can be suitably configured using at least one kind of curing catalyst.
In order to achieve a high colorant concentration, curing by reaction between epoxy groups is effective in addition to curing by reaction with the curing agent. In this case, it is preferable to use a curing catalyst without using a curing agent.

  Specific examples of the curing catalyst include those that are commercially available. For example, imidazole silane series IS-1000, IS-1000D, IM-1000, SP-1000, and IA manufactured by Japan Energy Co., Ltd. -1000A, the same IA-100P, the same IA-100F, the same IA-100AD, the same IA-100FD, the same IM-100F, the same IS-3000, the same IS-4000, etc. 1B2PZ made by Shikoku Kasei Co., Ltd., SFZ or the like is useful. However, it is not limited to these.

  When the curing catalyst is used, the addition amount of the curing catalyst in the colored layer is preferably about 1/10 to 1/1000 on a mass basis, more preferably about 150 to 200 epoxy equivalent epoxy resin. Is about 1/20 to 1/500, more preferably about 1/30 to 1/250, and it can be cured in a slight amount within the above range.

<solvent>
As described above, the colored layer is formed by using a colorant-containing photocurable composition prepared by including the above-described colorant and photocurable compound, and, if necessary, a binder, a curing agent, a curing catalyst, and the like. In general, a solvent can be used for the preparation of the colorant-containing photocurable composition. That is, the colorant-containing photocurable composition can be used as a solution (for example, a coating solution) in which various components are dissolved in a solvent.

  The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the colorant-containing photocurable composition are satisfied, especially considering the solubility, coating property, and safety of the dye and binder. Are preferably selected.

  Specifically, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

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 monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .;
Aromatic hydrocarbons such as toluene and xylene are preferred.

<Dispersant>
A dispersant can be added to improve the dispersibility of the pigment.
As the dispersant, known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorosurfactant, and a polymer dispersant.

  Furthermore, the graft copolymer described in JP-A-10-254133, which has a specific acid amide group-containing monomer and a quaternary ammonium salt monomer residue in the main chain, also has an excellent effect of finely dispersing the pigment. Since it has, it can be used as a dispersing agent. By using the graft copolymer, it is possible to finely disperse the pigment while reducing energy and time consumption, and the dispersed pigment does not agglomerate or settle with time. Dispersion stability over time can be maintained.

You may use a dispersing agent in combination of 2 or more types besides using individually by 1 type.
The addition amount of the dispersant in the colored layer (or the colorant-containing photocurable composition) is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

  Specific examples of various additives other than the above include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Cationic and anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrime Adhesion promoters such as xysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

-Preparation of a colorant-containing photocurable composition-
Hereinafter, the preparation method of the colorant containing photocurable composition used for formation of the colored layer of the image recording material which concerns on this invention is demonstrated. However, the present invention is not limited to this.

  When a pigment is used as the colorant, the pigment has a particle size distribution in the range described above, specifically, an average particle size in the range of 0.001 to 0.1 μm and a particle size distribution of 0.01 ±. It is preferable to use a dispersion in a sharp range of 0.005 μm, but the dispersion method is important for the adjustment. For example, a suitable dispersion method may be a roll mill such as a kneader or a two-roll. Examples of the dispersion method include a combination of dry dispersion (kneading dispersion treatment) for dispersion in a high viscosity state and wet dispersion (fine dispersion treatment) for dispersion in a relatively low viscosity state using a three-roll or bead mill. As the dispersion method, a method of co-dispersing two or more kinds of pigments, or not using a solvent or reducing the amount used in the kneading dispersion treatment, or using various dispersants is also suitable. Further, in order to relieve the solvent shock, it is preferable to add the resin component separately at the time of the kneading dispersion treatment and at the time of the fine dispersion treatment (use in two divisions), and shift from the kneading dispersion treatment to the fine dispersion treatment. In order to prevent reaggregation of the pigment particles, it is preferable to use a resin component having excellent solubility. Furthermore, it is also effective to use high hardness ceramics or beads with a small particle diameter for the beads of the bead mill used during the fine dispersion treatment. In addition, as said resin component, the above-mentioned alkali-soluble resin can be used, for example.

In the present invention, in particular, two or more kinds of pigments are used, and further, two or more kinds of pigments are dispersed in a high viscosity state of 50,000 mPa · s or more, and further dispersed in a low viscosity state of 1,000 mPa · s or less. It is preferable to use a colorant obtained in this manner.
In general, the pigment is supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization to dry, and a large amount of heat energy is given to dry it into a powder, the primary particles gather in the pigment. It is common to form aggregates (secondary particles).

  When a pigment is used as a colorant, first, a binder is added to the pigment so that the viscosity after the kneading and dispersing treatment is 50,000 mPa · s or more (preferably 50,000 to 100,000 mPa · s). The kneading and dispersing treatment is preferably performed. Here, the kneading dispersion treatment may be high viscosity dispersion or dry dispersion. Then, if necessary, a binder is additionally added to the dispersion after the kneading dispersion treatment, and the dispersion after the fine dispersion treatment is finely dispersed so that the viscosity becomes 1000 mPa · s or less (preferably 100 mPa · s or less). It is preferable to perform the treatment. The fine dispersion treatment may be low-viscosity dispersion or wet dispersion.

  In the kneading and dispersing treatment, the solvent ratio is preferably 0 to 20% by mass with respect to the dispersion. Dispersion without using a large amount of solvent can promote the wetting of the surface of the pigment particle with the constituent component mainly composed of the resin component of the vehicle, and the interface formed by the pigment particle surface is formed between the pigment particle and the air. From the solid / gas interface to the solid / solution interface between the pigment particles and the vehicle solution. When the interface formed by the surfaces of the pigment particles is converted from air to a solution and mixed and stirred, the pigment can be dispersed to a fine state close to the primary particles.

  Thus, in order to highly disperse the pigment, it is effective to convert the interface formed by the pigment particle surface from air to a solution. Such conversion requires a strong shearing force or compressive force. For this reason, in the said kneading | mixing dispersion | distribution process, it is preferable to use the thing of high viscosity as a to-be-kneaded material using the kneader which can exhibit strong shearing force and compressive force.

  In the fine dispersion treatment, it is preferable to mix and stir together with fine dispersion media such as glass or ceramic. Furthermore, it is preferable that the ratio of the solvent at the time of a fine dispersion process is 20-90 mass% of to-be-dispersed material. At the time of the fine dispersion treatment, since it is necessary to distribute the pigment particles uniformly and stably to a fine state, a disperser capable of imparting impact force and shear force to the agglomerated pigment particles; It is preferable to use a low-viscosity material.

  When a dye is used as the colorant, it is not necessary to disperse as described above, and it can be used after being dissolved in a solvent together with a binder.

  To the pigment dispersion or dye solution obtained as described above, a photocurable compound and, if necessary, a photopolymerization initiator are added, or when the binder itself is already a photocurable compound, A colorant-containing photocurable composition can be prepared by adding a photopolymerization initiator as necessary to impart a photocuring function and adding a solvent as necessary.

The color filter of the present invention is produced by the above-described method for producing a color filter of the present invention.
The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  In the present invention, the spin coater is adjusted to a higher colorant concentration (specifically, a concentration of 50% by mass or more based on the total solid content in the color layer or the colorant-containing photocurable composition). Applying uniform coating by slit coating, using photo-curing method instead of photolithography method, reducing solid content other than colorant as much as possible and realizing thin film, anisotropic pattern by dry etching method By forming a rectangular pattern while maintaining the properties, and a combination thereof, it is possible to obtain a thin film close to vapor deposition that could not be achieved conventionally, and to realize both rectangularity and adhesion.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

Example 1
<Preparation of a colorant-containing photocurable composition>
-Preparation of pigment dispersion-
For each color of green (G), blue (B), and red (R), each material shown in Table 1 below is uniformly kneaded with a kneader, and the kneaded product is then subjected to dry dispersion treatment (kneading dispersion treatment) with two rolls. did.
Next, 785 parts by mass of propylene glycol monomethyl ethyl acetate as a solvent component was added to the dispersion subjected to the dry dispersion treatment. Thereafter, the mixture was stirred with a homogenizer at 2000 rpm for 30 minutes to prepare a dispersion composition of each color of green (G), blue (B), and red (R) in which the pigment was uniformly dispersed. The obtained dispersion composition was finely dispersed with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads.

  Then, it filtered with a 2.5 micrometer filter, and obtained the pigment dispersion liquid (1)-(3) of each color in which the pigment was disperse | distributed uniformly. For each pigment dispersion, the viscosity of the kneaded product (dispersion) at the time of the kneading dispersion treatment and the fine dispersion treatment, and the average particle diameter and the particle diameter of 0.01 ± 0.005 μm in each pigment dispersion liquid Table 1 shows the ratio of the pigment particles. In addition, the particle diameter of the pigment was measured by using MICROTRAC UPA 150 manufactured by Nikkiso Co., Ltd. and using each of the colored resin compositions diluted with propylene glycol monomethyl ethyl acetate as a sample.

-Preparation of a colorant-containing photocurable composition-
Regarding the pigment dispersion liquid of each color in Table 1, 79.5 mass% for the pigment dispersion liquid (1), 73.2 mass% for the pigment dispersion liquid (2), and 80. Each of the following photocurable compounds and photopolymerization initiators was added so as to obtain a high pigment concentration of 0% by mass, and a colorant-containing photocurable composition (blue colorant-containing photocurable composition B, green A colorant-containing photocurable composition G and a red colorant-containing photocurable composition R) were prepared.

* Green colorant-containing photocurable composition G
The following composition was added to the pigment dispersion (1).
・ Dipentaerythritol hexaacrylate: 15 parts ・ Photopolymerization initiator: 3 parts (CGI-242, manufactured by Ciba Specialty Chemicals)
* Blue colorant-containing photocurable composition B
The following composition was added to the pigment dispersion (2).
Dipentaerythritol hexaacrylate: 10 parts Photopolymerization initiator: 3 parts (CGI-242, manufactured by Ciba Specialty Chemicals)
* Red colorant-containing photocurable composition R
The following composition was added to the pigment dispersion (3).
・ Dipentaerythritol hexaacrylate: 7 parts ・ Photopolymerization initiator: 3 parts (CGI-242, manufactured by Ciba Specialty Chemicals)

<Production of color filter>
Three silicon wafer substrates having an undercoat layer formed using “CT-2010L” manufactured by FUJIFILM Electronics Materials Co., Ltd. are prepared, and each of the colorant-containing photocurable compositions obtained from the above is prepared. After coating each undercoating layer of a separate silicon wafer substrate so as to form a coating film having a thickness of 0.5 μm by a spin coater, heat treatment was performed at 100 ° C. for 2 minutes using a hot plate, and the coating film was dried. A blue, green, or red colored layer was formed (colored layer forming step).

Next, using an i-line stepper (manufactured by Canon Inc.), the colored layer of each color was exposed on the entire surface with an exposure amount of 500 mJ / cm ² , and the colored layer was photocured (photocuring step).

  Next, a photoresist FHi-3950 (manufactured by FUJIFILM Electronics Materials; positive photoresist) was applied as an upper layer on the photocured colored layer of each color with a spin coater so as to have a film thickness of 1.5 μm. Thereafter, a heat treatment was performed at 100 ° C. for 2 minutes, followed by drying to form a resist layer (resist formation step).

Next, the formed resist layer is passed through a mask in a grid pattern of 1.5 μm × 1.5 μm size with an exposure amount of 200 mJ / cm ² using an i-line stepper (manufactured by Canon Inc.) from above the layer. Pattern exposure was performed. Then, for each color, the exposed resist layer was developed for 1 minute using a developer FHD-5 (manufactured by FUJIFILM Electronics Materials) to form an etching mask having a size of 1.5 μm × 1.5 μm. (Mask formation process).

For the colored layer of each color on which the etching mask is formed, dry etching of the colored layer with the non-mask portion exposed is performed with a mixed gas of a ratio of CF ₄ / O ₂ / Ar = 2/2/1 to form a color pattern. Formed. Thereafter, the resist layer that forms the etching mask is peeled off using a stripping solution MS-230 (manufactured by Fujifilm Electromaterials), and a 1.5 μm square color pattern having a high rectangularity (blue pattern, green pattern, Or a monochromatic color filter composed of a red pattern) was produced.

(Example 2)
-Formation of Blue pattern-
In the same manner as in Example 1, a blue pattern was formed.

-Formation of Green pattern-
Using a silicon wafer substrate on which a blue pattern is formed, the green colorant-containing photocurable composition G prepared as described above is applied to the side of the silicon wafer substrate on which the blue pattern is formed with a spin coater. The coating film was dried to form a colored layer (G layer) for forming a green pattern having a layer thickness of 0.5 μm. Subsequently, using an i-line stepper (Canon Co., Ltd.), and the entire surface exposure of the G layer by the exposure amount of 800 mJ / cm ^2, and overall exposure further an exposure amount of 650 mJ / cm ^2, light of G layer Cured.

  Subsequently, on the photocured G layer (colored layer), a photoresist FHi-3950 (manufactured by FUJIFILM Electronics Materials; positive photoresist) was applied with a spin coater so as to have a film thickness of 1.5 μm. A resist layer was formed in the same manner as in Example 1.

Using the i-line stepper (manufactured by Canon Inc.) from above the formed resist layer, the pattern is passed through a mask in a grid shape of 1.5 μm × 1.5 μm size with an exposure amount of 200 mJ / cm ^2. Exposure is performed, and the exposed resist layer is developed to form an etching mask having a size of 1.5 μm × 1.5 μm, and dry etching of the exposed colored layer in the non-mask portion is performed in the same manner as in Example 1. The second green pattern was formed on the silicon wafer substrate. Thereafter, the resist layer that forms an etching mask remaining on the G layer was peeled off using a peeling solution MS-230 (manufactured by Fuji Film Electromaterials) and removed.

-Formation of Red pattern-
From the above, using a silicon wafer substrate on which a blue pattern and a green pattern are formed, the red colorant-containing photocurable composition R prepared as described above is formed into the blue pattern and the green pattern on the silicon wafer substrate. After further coating on the coated side, heat treatment was performed at 100 ° C. for 2 minutes using a hot plate to dry the coating film (dry layer thickness 0.5 μm), and then an i-line stepper (manufactured by Canon Inc.) ) Was used to expose the entire surface with an exposure amount of 800 mJ / cm ² , and the R layer (colored layer) was photocured.
Subsequently, the photocured R layer is dry-etched with O ₂ gas to remove the R layer existing on the Blue pattern and the Green pattern, and further planarized by using a CMP (Chemical Mechanical Polishing) technique. A third red pattern was formed.
As described above, the color filter of the present invention for three colors of RGB was produced. In addition, the color filter was excellent in adhesion without causing peeling in the process until the third color was formed.

(Example 3)
In Example 2, the PY-139 (colorant) in the pigment dispersion (1) used for the preparation of the green colorant-containing photocurable composition G was replaced with PY-150, and CT-2010L of a silicon wafer substrate. In the same manner as in Example 2 except that the undercoat layer made of Si is composed of a SiN film, and the dry etching treatment of the G layer is performed by changing the etching gas to a mixed gas of CO ₂ / O ₂ = 1/1. Thus, RGB color filters were produced.

Example 4
In Example 2, the blue colorant-containing photocurable composition B, the green colorant-containing photocurable composition G, and the red colorant-containing photocurable composition R were respectively converted into the following blue dye-containing light. A RGB color filter was produced in the same manner as in Example 2 except that the curable composition B2, the green dye-containing photocurable composition G2, and the red dye-containing photocurable composition R2 were used. .

* Composition of green (G) dye-containing photocurable composition G2 · Acid Green 25 · · 115 parts · Acid Yellow 17 · · 40 parts · Dipentaerythritol hexaacrylate · · 25 parts · Photopolymerization initiator ... 20 parts (CGI-124, manufactured by Ciba Specialty Chemicals)

* Composition of blue (B) dye-containing photocurable composition-Acid Blue 23 ... 125 parts-Acid violet 7 ... 25 parts-Dipentaerythritol hexaacrylate-20 parts-Photopolymerization initiator- ..20 parts (CGI-124, manufactured by Ciba Specialty Chemicals)

* Composition of red (R) dye-containing photocurable composition-Acid Red 8 ... 80 parts-Acid Yellow 34 ... 20 parts-Dipentaerythritol hexaacrylate-15 parts-Photopolymerization initiator- ..10 parts (CGI-242, manufactured by Ciba Specialty Chemicals)

(Comparative Example 1)
<Preparation of a colorant-containing photocurable composition>
-Preparation of pigment dispersion-
In the same manner as in “—Preparation of pigment dispersion liquid” in Example 1, a pigment dispersion liquid having the composition shown in Table 2 below was prepared.

-Preparation of a colorant-containing photocurable composition-
About the pigment dispersion of each color in Table 2 above, the following composition was added and mixed uniformly with a stirrer to give a high pigment concentration colorant with a photolithographic function so that the same pigment concentration as in Example 1 was obtained. Containing photocurable compositions (blue colorant-containing photocurable composition B3, green colorant-containing photocurable composition G3, and red colorant-containing photocurable composition R3) were prepared.

* Green colorant-containing photocurable composition G3
The following composition was added to the green pigment dispersion (4).
・ Dipentaerythritol pentaacrylate (monomer): 10 parts ・ Propylene glycol monomethyl ethyl acetate (solvent): 120 parts ・ Ethyl-3-ethoxypropionate (solvent): 50 parts ・ Halomethyltriazine series Initiator ... 2 parts

* Blue colorant-containing photocurable composition B3
The following composition was added to the blue pigment dispersion (5).
・ Dipentaerythritol pentaacrylate (monomer) 7 parts ・ Propylene glycol monomethyl ethyl acetate (solvent) 100 parts ・ Ethyl-3-ethoxypropionate (solvent) 40 parts ・ Halomethyltriazine series Initiator ... 2 parts

* Red colorant-containing photocurable composition R3
The following composition was added to the red pigment dispersion (6).
・ Dipentaerythritol pentaacrylate (monomer): 5 parts ・ Propylene glycol monomethyl ethyl acetate (solvent): 70 parts ・ Ethyl-3-ethoxypropionate (solvent): 30 parts ・ Halomethyltriazine series 1 part of initiator

  Three silicon wafer substrates having an undercoat layer coated and cured with “CT-2000L” manufactured by FUJIFILM Electronics Materials Co., Ltd. were prepared, and each of the colorant-containing photocurable compositions obtained above was After coating so that a 0.5 μm-thick coating film is formed on each undercoat layer of a separate silicon wafer substrate by a spin coater, heat treatment is performed at 100 ° C. for 2 minutes on a hot plate to dry the coating film I let you.

Next, using an i-line stepper (Canon Co., Ltd.), pattern exposure was performed through a mask in a grid shape of 1.5 μm × 1.5 μm size with an exposure amount of 200 mJ / cm ² , and then an alkaline developer CD- Development processing was performed with 2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.).
At this time, all colors were dissolved and pattern formation could not be performed. That is, in the high pigment concentration region, it is clear that the photo-curing system is optimal for pattern formation by dry etching, which is suitable for thinning.

(Evaluation)
The following evaluation was performed about each Example and the comparative example. The evaluation results are shown in Table 3 below. In addition, about the comparative example, the result was shown about the item which could be evaluated.
-1. Rectangularity
The photograph which image | photographed the cross-sectional shape of the obtained color filter with the scanning electron microscope (SEM) was observed, and it evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
A: The cross section was a rectangular shape with a good cross section.
X: The cross section had a taper shape etc., and a favorable rectangular shape was not obtained.

-2. Developability
The presence or absence of dissolution of the colored layer and the presence or absence of image defects during peeling and removal of the etching mask were visually evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: Dissolution of the colored layer and image defects were not observed.
X: Dissolution of the colored layer and image defects were observed.

-3. Surface properties (surface condition)
The surface state of the color filter after removal of the etching mask was observed with a photograph taken with a scanning electron microscope (SEM) and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
A: Almost no irregularities were observed on the surface and side surfaces of the color filter.
Δ: Clear irregularities were observed on the surface and side surfaces of the color filter.
X: On the surface and side surfaces of the color filter, not only irregularities but also holes and defects were observed.

-4. Adhesion
About the obtained color filter, the abrasion resistance by CMP (Chemical Mechanical Polishing) technique was evaluated according to the following evaluation criteria about the adhesiveness with the silicon wafer substrate (specifically undercoat layer) of the color pattern of each color.
〔Evaluation criteria〕
○: No peeling was observed.
Δ: Peeling was observed in the range of less than 20%.
X: Peeling was observed in the range of 20% or more.

As shown in Table 3, in the examples, a color filter having excellent spectral characteristics, excellent surface properties, excellent pattern rectangularity, and high adhesion to each color pattern substrate is prepared. I was able to. Further, as shown in Example 3, not only when a pigment is used as a colorant, but also when a dye is used, etching is possible, and an RGB three-color filter can be manufactured.
In the above comparative example, the colored layer is not dissolved and pattern formation is possible for all colors, and in areas where the colorant is highly concentrated, the pattern is formed by dry etching with a photo-curing system as in the example. It was optimal to carry out and was effective for thinning.

Claims (2)

(1) A colorant-containing photocurable composition containing a colorant and a photocurable compound and having a concentration of the colorant in the total solid content of 50% by mass or more and less than 100% by mass is provided on a substrate. Forming a colored layer;
(2) a step of exposing and curing the colored layer formed on the substrate;
(3) providing a photosensitive resin composition on the cured colored layer to form a photosensitive resin layer;
(4) exposing at least the photosensitive resin layer imagewise and developing to form a pattern comprising the photosensitive resin layer;
(5) subjecting the colored layer to a dry etching process using the pattern as a mask to form a colored pattern;
A method for producing a color filter comprising:   A color filter produced by the method for producing a color filter according to claim 1.