TW202022054A - Coloring composition, film, method for producing color filter, color filter, solid state imaging device and image display device - Google Patents

Abstract

Provided is a coloring composition which contains a coloring agent, a resin and an organic solvent. The coloring agent is contained at a quantity of 50 mass% or more relative to the total solid content in the coloring composition. The coloring agent contains 40 mass% or more of a pigment A for which the major axis length/minor axis length ratio is 1.4 or more. Also provided are a film which uses the coloring composition; a method for producing a color filter; a color filter; a solid state imaging device; and an image display device.

Description

Coloring composition, film, method for manufacturing color filter, color filter, solid-state imaging element and image display device

The present invention relates to a coloring composition containing pigment. In addition, the present invention relates to a film using a colored composition, a method of manufacturing a color filter, a color filter, a solid-state imaging device, and an image display device.

In recent years, due to the popularization of digital cameras and mobile phones with cameras, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as the core components of displays or optical components. The color filter is manufactured using a coloring composition containing colorants such as pigments.

Patent Document 1 describes a step of forming colored pixels of a color filter using a coloring composition for image formation. The coloring composition for image formation contains a pigment and an adhesive component as essential components, and the pigment When the short diameter of the primary particles is set to a and the long diameter is set to b, the content of primary particles satisfying formula (1) is 70% by volume or more and the content of primary particles satisfying formula (2) is 5% by volume or less The shape distribution. b/a＜1.4……（1） b/a≧1.8……（2）

On the other hand, Patent Document 2 describes an invention relating to a pigment ink composition used for inkjet printing inks, etc., the pigment ink composition containing pigment particles containing at least needle-shaped pigment particles , Dispersant and solvent, needle-like pigment particles are composed of needle-like shapes with an aspect ratio of 3 or more, with an average aspect ratio of 5 or more and 7 or less, and an average minor diameter of 20 nm or more and 30 nm or less, and the standard deviation of the minor diameter is The distribution is below 2.0nm, and the acicular pigment particles are coated with a dispersant. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-239835 [Patent Document 2] JP 2009-221266 A

According to the research of the present inventors, it is known that a film formed using a coloring composition containing a pigment is prone to film shrinkage. It is known that film shrinkage tends to occur particularly in an environment with high humidity.

If the film shrinks, it is easy to create gaps between adjacent members. For example, when a coloring composition containing a pigment is used to form a pixel of a color filter, if the pixel shrinks and the line width of the pixel decreases, there may be gaps between adjacent pixels, which may cause the sensitivity of the device to change. .

Therefore, the object of the present invention is to provide a colored composition capable of forming a film that inhibits film shrinkage. In addition, the present invention provides a film using the colored composition, a method of manufacturing a color filter, a color filter, a solid-state imaging device, and an image display device.

According to the research of the present inventor, it was found that the above-mentioned object can be achieved by the following configuration, thereby completing the present invention. In this way, the present invention provides the following. <1> A coloring composition comprising a colorant, a resin and an organic solvent, wherein The total solid content of the coloring composition contains 50% by mass or more of coloring agent, The colorant contains pigment A having a ratio of the minor axis length to the major axis length of 40% by mass or more, that is, the value of the major axis length/minor axis length is 1.4 or more. <2> The colored composition as described in <1>, wherein The coloring composition contains 60% by mass or more of the coloring agent in the total solid content. <3> The coloring composition as described in <1> or <2>, wherein The value of the major axis length/minor axis length of the pigment A is 1.4 or more and 3.0 or less. <4> The colored composition according to any one of <1> to <3>, wherein The average length of the major axis of the pigment A is 15 to 150 nm. <5> The colored composition according to any one of <1> to <4>, wherein The average value of the minor axis length of the pigment A is 10-100 nm. <6> The colored composition according to any one of <1> to <5>, wherein Pigment A is a red pigment. <7> The colored composition as described in <6>, wherein The red pigment is at least one selected from the group consisting of Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272. <8> The colored composition according to any one of <1> to <7>, which contains a photopolymerization initiator and a polymerizable compound. <9> The colored composition according to any one of <1> to <8>, wherein The resin includes an alkali-soluble resin. <10> The colored composition according to any one of <1> to <9>, which is used to form a pattern by a photolithography method. <11> The colored composition according to any one of <1> to <10>, which is used in a solid-state imaging device. <12> The colored composition according to any one of <1> to <10>, which is used in a color filter. <13> The colored composition as described in <12>, which is used to form red pixels. <14> A film obtained from the colored composition described in any one of <1> to <13>. <15> A method for manufacturing a color filter, which has: The step of using the colored composition described in any one of <1> to <13> to form a colored composition layer on the support; and The step of patterning the colored composition layer by photolithography. <16> A color filter having the film described in <14>. <17> A solid-state imaging device having the film described in <14>. <18> An image display device having the film described in <14>. [Effect of invention]

According to the present invention, it is possible to provide a coloring composition capable of forming a film that inhibits film shrinkage, a method of manufacturing a film, a color filter, a color filter, a solid-state imaging device, and an image display device.

Hereinafter, the content of the present invention will be described. In this specification, "～" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit. In the label of the group (atomic group) in this specification, the label not marked with substituted and unsubstituted includes a group (atomic group) without a substituent, and also includes a group (atomic group) with a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used in the exposure, actinic rays or radiation such as the bright-ray spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, "(meth)acrylate" means both or either acrylate and methyl acrylate, "(meth)acrylic" means both or either acrylic acid and methacrylic acid, and "(meth)acrylate ) "Acrylic group" means both or either of an acrylic group and a methacryl group. In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, weight average molecular weight and number average molecular weight are polystyrene conversion values measured by GPC (gel permeation chromatography) method. In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In this specification, pigments refer to compounds that are difficult to dissolve in solvents. For example, the solubility of the pigment in 100 g of water at 23° C. and 100 g of propylene glycol monomethyl ether acetate at 23° C. is preferably 0.1 g or less, and more preferably 0.01 g or less. In this specification, the term "step" is not only an independent step, but even if it cannot be clearly distinguished from other steps, as long as it achieves the desired effect for the step, it is also included in this term.

＜Coloring composition＞ The coloring composition of the present invention, which includes a coloring agent, a resin and an organic solvent, is characterized by: The total solid content of the coloring composition contains 50% by mass or more of coloring agent, The colorant contains pigment A having a ratio of the minor axis length to the major axis length of 40% by mass or more, that is, the value of the major axis length/minor axis length is 1.4 or more.

According to the coloring composition of the present invention, by containing 50% by mass or more of the coloring agent containing 40% by mass or more of the pigment A in the total solid content of the coloring composition, shrinkage of the obtained film can be suppressed. It is presumed that the pigment A is densely spread in the obtained film, and as a result, it is presumed that the shrinkage of the obtained film can be suppressed. In particular, even when the film is exposed to an environment with high humidity for a long time, shrinkage of the film can be effectively suppressed. In addition, the coloring composition of the present invention contains 50% by mass or more of a coloring agent, and therefore can form a film with a high color value. Therefore, the desired spectral characteristics are maintained, and thinning can be achieved.

In the present invention, the value of the major axis length/minor axis length of the pigment A is preferably 1.4 or more and 3.0 or less. According to this aspect, when the colored composition of the present invention is used and the pattern is formed by the photolithography method, the generation of development residue can be suppressed, and a pattern with good rectangularity can be formed.

In the present invention, the pigment A is preferably a red pigment. Red pigments generally tend to have lower color values. However, as red pigments, use those with a major axis length/minor axis length of 1.4 or more, so that the film can be densely covered with red pigments, and red pigments can also be formed. High color film.

The colored composition of the present invention can be suitably used as a colored composition for solid-state imaging devices. In addition, the colored composition of the present invention can be suitably used as a colored composition for color filters. Specifically, it can be preferably used as a coloring composition for forming a pixel of a color filter, and can be more preferably used as a coloring composition for forming a pixel of a color filter used in a solid-state imaging device. Examples of the pixels of the color filter include colored pixels such as red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. The coloring composition of the present invention can be preferably used as a coloring composition for forming a red pixel.

The coloring composition of the present invention can be preferably used for pattern formation by photolithography. In these cases, the coloring composition of the present invention preferably contains a photopolymerization initiator and a polymerizable compound. Moreover, it is preferable that the resin contained in a coloring composition contains an alkali-soluble resin.

In addition, the coloring composition of the present invention can also be used as a composition for forming color microlenses. As a manufacturing method of the color microlens, the method described in JP 2018-010162 A, etc. can be mentioned.

Hereinafter, each component used in the coloring composition of the present invention will be described.

＜＜Colorant＞＞ The coloring composition of the present invention contains a coloring agent. As a coloring agent, color coloring agents, such as a red coloring agent, a green coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, and an orange coloring agent, are mentioned. Examples of the colorant include pigments and dyes, and those containing pigments can be used. The pigment may be any of inorganic pigments and organic pigments. Moreover, it is also possible to use a material obtained by replacing part of an inorganic pigment or an organic-inorganic pigment with an organic chromophore. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be easily performed.

The coloring agent used in the present invention contains 40% by mass or more of pigment A (hereinafter, also referred to as pigment A) whose ratio of the minor axis length to the major axis length, that is, the value of the major axis length/minor axis length is 1.4 or more. The value of the major axis length/minor axis length of the pigment A is preferably 1.4 or more and 3.0 or less. If the value of the major axis length/minor axis length of the pigment A is within the above range, it is easy to obtain a film having a high color value and suppressing film shrinkage. Furthermore, when the coloring composition of the present invention is used and the pattern is formed by the photolithography method, the generation of development residue can be suppressed, and a pattern with good rectangularity can also be formed.

For the reason that it is easy to obtain a film that suppresses light scattering and has high brightness, the upper limit of the value of the major axis length/minor axis length of the pigment A is preferably 2.7 or less, and more preferably 2.4 or less. In addition, from the viewpoint of making it easier to spread the pigment densely in the film, the lower limit of the value of the major axis length/minor axis length of the pigment A is preferably 1.6 or more, more preferably 1.8 or more, and more preferably 2.0 or more.

The average value of the minor axis length of the pigment A is preferably 10 to 100 nm. From the viewpoint of the reliability of the heat resistance, moisture resistance, weather resistance and the like of the obtained film, the lower limit is preferably 15 nm or more, more preferably 20 nm or more, and more preferably 30 nm or more. From the viewpoint of the color value, the upper limit is preferably 70 nm or less, more preferably 50 nm or less, and more preferably 40 nm or less.

The average value of the major axis length of the pigment A is preferably 15 to 150 nm. From the viewpoint of reliability, the lower limit is preferably 20 nm or more, and more preferably 30 nm or more. From the viewpoint of the color value, the upper limit is preferably 100 nm or less, more preferably 70 nm or less, and more preferably 50 nm or less.

In addition, in this specification, the length of the major axis and the length of the minor axis are values measured by the following method. That is, using a scanning electron microscope, the image obtained by shooting at an acceleration voltage of 5kV and an imaging magnification of 100,000 times is digitized, and the image brightness data in the long axis direction and the short axis direction of the particles (from the long axis The coordinates of the direction, the coordinates of the minor axis, and the brightness are composed of three components.). In digitization, the image is divided into 1280 in the width direction and processed with 8 bits of brightness to obtain 256 gray-scale data, and the image brightness of each divided coordinate point is converted into a predetermined gray-scale value. Next, in the obtained image brightness data, the coordinates of the direction corresponding to the long axis of the particle are set as the horizontal axis, and the average value of the brightness at each coordinate point in the long axis direction (that is, divided into 1280) The average value of the brightness in the coordinate points) is set as the vertical axis to create a brightness curve. Differentiate the created brightness curve to create a differential curve, and determine the coordinates of the particle's boundary from the peak position of the created differential curve. Repeat the operation of setting the coordinates of the direction corresponding to the long axis of the particle to the horizontal axis 3 times, and set the longest axis length to the long axis length. Repeat the operation of setting the coordinates as the horizontal axis 3 times in the minor axis direction, and set the shortest axis length as the minor axis length. Specifically, the length of the major axis refers to the length of an axis (straight line) that can take the length of the longest particle as the major axis. On the other hand, the short axis refers to an axis determined to be the longest length when the particle length is taken on a straight line orthogonal to the long axis, and the length of this axis is defined as the short axis length.

In addition, the average value of the minor axis length of the pigment A and the average value of the major axis length of the pigment A are the arithmetic averages of the minor axis length and the major axis length of 100 pigment A.

As a method of adjusting the value of the major axis length/minor axis length of the pigment, there can be mentioned the method of adjusting the grinding conditions of the pigment to adjust the value of the major axis length/minor axis length, and adjusting the type and amount of the particle growth inhibitor. The method of grinding treatment to adjust the value of the long axis length/short axis length, the method of heating and aging the pigment to adjust the value of the long axis length/short axis length, etc. As the particle growth inhibitor, the compound described in paragraphs 0041 to 0050 of JP 2009-221266 A can be cited.

As the type of the pigment used in the present invention, the following can be mentioned.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 231, 232 (methine/polymethine series), etc. (above are yellow pigments), CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 Etc. (the above are orange pigments), C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (the above are green pigments), C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (dibenzopyran series), etc. (the above are purple pigments), CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo Series), 88 (methine/polymethine series), etc. (the above are blue pigments), CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 279, 294 (dibenzo Piperanes, Organo Ultamarine, Bluish Red, etc. (the above are red pigments).

In addition, as a green pigment, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. As a specific example, the compound described in International Publication WO2015/118720 can be mentioned. Moreover, as a green pigment, the compound described in CN106909027A, the phthalocyanine compound which has a phosphoric acid ester as a ligand, etc. can also be used.

In addition, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. As specific examples, the compounds described in paragraphs 0022 to 0030 of JP 2012-247591 and paragraph 0047 of JP 2011-157478 can be cited.

In addition, as the yellow pigment, the pigments described in JP 2017-201003 A, the pigments described in JP 2017-197719, and paragraphs 0011 to 0062 of JP 2017-171912 can also be used. , Pigments described in paragraphs 0137 to 0276, JP 2017-171913 paragraphs 0010 to 0062, 0138 to 0295 paragraphs, JP 2017-171914 paragraphs 0011 to 0062, 0139 The pigment described in paragraph 0190, and the pigment described in paragraphs 0010 to 0065 and paragraph 0142 to 0222 of JP 2017-171915 A.

Moreover, as the yellow pigment, the compound described in JP 2018-062644 can also be used. The compound can also be used as a pigment derivative.

In addition, as red pigments, diketopyrrolopyrrole pigments having at least one bromine atom substituted in the structure described in JP 2017-201384 A, as described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 can also be used. Recorded diketopyrrolopyrrole pigments, etc. In addition, as the red pigment, a compound having a structure in which an aromatic ring group formed by introducing a group bonding an oxygen atom, a sulfur atom, or a nitrogen atom to the aromatic ring is bonded to the diketopyrrolopyrrole skeleton can also be used.

The pigment A used in the present invention preferably contains a red pigment. Moreover, it is also preferable that the red pigment is a diketopyrrolopyrrole compound. The red pigment is preferably at least one selected from the group consisting of Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272, and more preferably Color Index Pigment Red 272. Red pigments generally tend to have a low color value. However, as a red pigment, a long-axis length/short-axis length value of 1.4 or more can be used to form a film with a high red color value.

In the present invention, dyes can also be used in colorants. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo series, anilino azo series, triaryl methane series, anthraquinone series, anthrapyridine quinone series, benzylidene series, oxacyanine series, pyrazolotriazole azo series, Pyridone azo series, cyanine series, phenanthrazine series, pyrrolopyrazole methine azo series, dibenzopyran series, phthalocyanine series, benzopyran series, indigo series, pyrromethene Department of other dyes. In addition, the thiazole compound described in JP 2012-158649 A, the azo compound described in JP 2011-184493 A, and the azo compound described in JP 2011-145540 A can also be preferably used. The azo compound. In addition, as the yellow dye, the quinoline yellow compound described in paragraphs 0011 to 0034 of JP 2013-054339 A, and the quinoline described in paragraphs 0013 to 0058 of JP 2014-026228 A can also be used. Yellow compounds and so on.

In the present invention, pigment multimers can also be used in the colorant. The pigment polymer is preferably used as a dye dissolved in a solvent, but the pigment polymer can form particles. When the pigment polymer is a particle, it is usually used in a state dispersed in a solvent. The pigment multimer in the particle state can be obtained, for example, by emulsion polymerization, and as a specific example, the compound and the production method described in JP 2015-214682 A can be cited. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but can also be 100 or less. The plurality of pigment structures in a molecule can be the same pigment structure or different pigment structures. The weight average molecular weight (Mw) of the pigment polymer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and more preferably 20,000 or less. The pigment polymer can also use Japanese Patent Application Publication No. 2011-213925, Japanese Patent Application Publication No. 2013-041097, Japanese Patent Application Publication No. 2015-028144, Japanese Patent Application Publication No. 2015-030742, and International Publication No. WO2016/031442 The compound described in etc.

The content of the coloring agent is 50% by mass or more in the total solid content of the coloring composition, preferably 53% by mass or more, more preferably 59% by mass or more, and even more preferably 62% by mass or more. The upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.

In the coloring agent used in the coloring composition of the present invention, the content of the pigment is 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass % Or more is more preferable, 90 mass% or more is still more preferable, and 95 mass% or more is particularly preferable. The upper limit can be set to 100% by mass. In addition, it is also preferable that the coloring agent used in the coloring composition of the present invention is substantially only a pigment. The case where the colorant is substantially only a pigment means that the content of the pigment is 99% by mass or more, preferably 99.5% by mass or more, and it is particularly preferable that only the pigment is used. When the coloring agent used in the coloring composition of the present invention contains two or more kinds of pigments, at least one of the two or more kinds of pigments may be the above-mentioned pigment A, but all the pigments contained in the coloring agent are The above-mentioned pigment A is preferable.

In the coloring agent used in the coloring composition of the present invention, the content of the above-mentioned pigment A (the ratio of the minor axis length to the major axis length, that is, the pigment whose major axis length/minor axis length is 1.4 or more) is 40 mass % Or more, 50 mass% or more is preferred, 60 mass% or more is more preferred, 70 mass% or more is more preferred, 80 mass% or more is more preferred, 90 mass% or more is more preferred, 95 mass% or more Above% is particularly good. The upper limit can be set to 100% by mass. In addition, it is also preferable that the coloring agent used in the coloring composition of the present invention is substantially only pigment A. The case where the colorant is substantially only pigment A means that the content of pigment A is 99% by mass or more, preferably 99.5% by mass or more, and only pigment A is particularly preferable.

In the coloring composition of the present invention, the content of the pigment in the total solid content of the coloring composition is preferably 50% by mass or more, more preferably 53% by mass or more, more preferably 59% by mass or more, and 62% by mass or more It is especially good. The upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.

＜＜Resin＞＞ The coloring composition of the present invention contains a resin. The resin is blended for the purpose of dispersing the pigment in the coloring composition or the use of an adhesive, for example. In addition, the resin used mainly for dispersing pigments is also called dispersant. However, these uses of resin are an example, and it can also be used for purposes other than these uses.

The weight average molecular weight (Mw) of the resin is preferably 3000-2000000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polyether resins, polyether sulfide resins, polyphenylene resins, and polyarylene resins. Ether phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. From these resins, one type may be used alone, or two or more types may be mixed and used. In addition, the resins described in paragraphs 0041 to 0060 of JP 2017-206689 A and the resins described in paragraphs 0022 to 0071 of JP 2018-010856 A can also be used.

In the present invention, it is preferable to use a resin having an acid group as the resin. According to this aspect, the developability of the colored composition can be improved, and it is easy to form pixels with excellent rectangularity. As an acid group, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group, etc. are mentioned, and a carboxyl group is preferable. A resin having an acid group can be used as an alkali-soluble resin, for example.

It is preferable that the resin having an acid group contains a repeating unit having an acid group on the side chain, and it is more preferable to include 5 to 70 mol% of all the repeating units of the resin having an acid group on the side chain. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

The resin having an acid group includes a compound derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers" .) The repeating unit of the monomer component is also preferred.

[Chemical Formula 1]

式（ED2）中，R表示氫原子或碳數1～30的有機基團。關於式（ED2）的詳細內容，能夠參閱日本特開2010-168539號公報的記載，該內容被編入到本說明書中。In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms. [Chemical Formula 2]

In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Regarding the details of the formula (ED2), refer to the description in Japanese Patent Application Laid-Open No. 2010-168539, which is incorporated into this specification.

As a specific example of the ether dimer, for example, the description in paragraph 0317 of JP 2013-029760 A can be referred to, and this content is incorporated in this specification.

式（X）中，R₁ 表示氫原子或甲基，R₂ 表示碳數2～10的伸烷基，R₃ 表示氫原子或可以包含苯環之碳數1～20的烷基。n表示1～15的整數。It is also preferable that the resin used in the present invention contains a repeating unit derived from a compound represented by the following formula (X). [Chemical formula 3]

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may contain a benzene ring. n represents an integer of 1-15.

Regarding the resin having an acid group, refer to the description in paragraphs 0558 to 0571 of JP 2012-208494 (corresponding to paragraphs 0685 to 0700 of the specification of U.S. Patent Application Publication No. 2012/0235099), and Japanese Patent Application Publication No. 2012-198408 The descriptions in paragraphs 0076 to 0099 of the Bulletin are incorporated into this manual. Moreover, the resin which has an acid group can also use a commercial item.

The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5,000 to 100,000. Furthermore, the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.

Examples of resins having acid groups include resins having the following structures. [Chemical formula 4]

The coloring composition of the present invention can also contain a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (alkaline resins). Here, the acidic dispersant (acidic resin) means a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is set to 100 mol%, and essentially only contains acid The base resin is better. The acidic carboxyl group possessed by the acidic dispersant (acidic resin) is preferred. The acid value of the acidic dispersant (acid resin) is preferably 40-105 mgKOH/g, more preferably 50-105 mgKOH/g, and still more preferably 60-105 mgKOH/g. In addition, the basic dispersant (basic resin) means a resin in which the amount of basic groups is greater than the amount of acid groups. The alkaline dispersant (alkaline resin) is preferably a resin in which the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and the amount of basic groups exceeds 50 mol%. The basic amino group possessed by the basic dispersant is preferably.

The resin used as the dispersant preferably contains a repeating unit having an acid group. Since the resin used as a dispersant contains a repeating unit having an acid group, it is possible to more suppress the generation of development residue when patterning by photolithography.

It is also preferable that the resin used as the dispersant is a graft resin. For the details of the graft resin, reference can be made to the description in paragraphs 0025 to 0094 of JP 2012-255128 A, and this content is incorporated in this specification.

The resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. As a polyimine-based dispersant, a resin having a main chain and a side chain, and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred. The main chain contains a functional group having a pKa of 14 or less. Partial structure, the number of atoms in the side chain is 40 to 10,000. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP 2012-255128 A can be referred to, and the content is incorporated in this specification.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core. Examples of such resins include dendrimers (including star polymers). In addition, as specific examples of dendrimers, polymer compounds C-1 to C-31 and the like described in paragraphs 0196 to 0209 of JP 2013-043962 A can be cited.

Moreover, the resin (alkali-soluble resin) which has the said acid group can also be used as a dispersing agent.

In addition, the resin used as a dispersant is preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in the side chain. The content of repeating units having ethylenically unsaturated bond groups in the side chain is preferably 10 mol% or more of all repeating units of the resin, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol% Better.

The dispersant can also be obtained as a commercially available product. Specific examples of this include the DISPERBYK series manufactured by BYK Chemie GmbH (for example, DISPERBYK-111, 161, etc.), and the SOLSPERSE series manufactured by Lubrizol Japan Limited. (for example, SOLSPERSE76500, etc.) )Wait. In addition, the pigment dispersant described in paragraphs 0041 to 0130 of JP 2014-130338 A can also be used, and this content is incorporated in this specification. In addition, the resin explained as the above-mentioned dispersant can also be used for purposes other than the dispersant. For example, it can also be used as an adhesive.

The content of the resin in the total solid content of the coloring composition is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less. In addition, the content of the acid group-containing resin (alkali-soluble resin) in the total solid content of the coloring composition is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less. In addition, for the reason that it is easy to obtain excellent developability, the content of the acid group-containing resin (alkali-soluble resin) in the total resin is preferably 30% by mass or more, more preferably 50% by mass or more, and 70% by mass The above is more preferable, and 80% by mass or more is particularly preferable. The upper limit may be 100% by mass, 95% by mass, or 90% by mass or less.

＜＜Organic solvent＞＞ The coloring composition of the present invention contains an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For details of these, please refer to paragraph 0223 of International Publication WO2015/166779, which is incorporated into this specification. In addition, an ester-based solvent substituted with a cyclic alkyl group and a ketone-based solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, 3-ethoxy methyl propionate, ethyl 3-ethoxy propionate, and ethyl cellosolve acetate. , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N'-dimethylpropanamide, 3-butoxy- N,N'-Dimethylpropanamide and so on. Among them, for environmental reasons, it may be preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents (for example, relative to the total amount of organic solvents) It can be set to 50 mass ppm (parts per million: one part per million) or less, can also be set to 10 mass ppm or less, or can be set to 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent with a small metal content, and the metal content of the organic solvent is preferably 10 parts per billion (parts per billion) or less by mass, for example. According to needs, organic solvents of quality ppt (parts per trillion: parts per trillion) can be used, such organic solvents are provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015), for example.

As a method for removing impurities such as metals from organic solvents, for example, distillation (molecular distillation or thin film distillation, etc.) or filtration using a filter can be cited. As the filter pore size of the filter used for filtration, 10 μm or less is preferable, 5 μm or less is more preferable, and 3 μm or less is more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

Organic solvents can contain isomers (compounds with the same number of atoms but different structures). In addition, the isomer may contain only one kind or plural kinds.

In the present invention, it is preferable that the peroxide content in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the peroxide content is not substantially contained.

The content of the organic solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and more preferably 30 to 90% by mass.

Furthermore, from the viewpoint of environmental control, it is preferable that the colored composition of the present invention does not substantially contain environmental control substances. In addition, in the present invention, substantially no environmentally regulated substances means that the content of environmentally regulated substances in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less, and 10 mass ppm or less is more preferably, 1 mass ppm Below ppm is particularly good. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene. These are registered as environmentally controlled substances in accordance with REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, PRTR (Pollutant Release and Transfer Register) law, and VOC (Volatile Organic Compounds) control, and their usage and operation methods are strictly controlled. These compounds may be used as a solvent when manufacturing the components used in the coloring composition of the present invention, and may be mixed into the coloring composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is better to reduce these substances as much as possible. As a method of reducing environmentally regulated substances, there is a method of heating or depressurizing the inside of the system to make it above the boiling point of the environmentally regulated substances and distilling and removing the environmentally regulated substances from the system to reduce them. In addition, when a small amount of environmentally regulated substances is removed by distillation, it is also useful to azeotrope with a solvent having a boiling point equal to the solvent in order to improve efficiency. In addition, when a compound having radical polymerizability is contained, in order to suppress the radical polymerization reaction during the vacuum distillation removal and cross-linking between molecules, a polymerization inhibitor or the like may be added to perform vacuum distillation removal. These distillation removal methods can be used in the stage of raw materials, the stage of products obtained by reacting the raw materials (such as polymerized resin solution and polyfunctional monomer solution), or the stage of coloring composition produced by mixing these compounds, etc. In any stage of the

＜＜Polymerizable compound＞＞ The coloring composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by radicals, acid, or heat can be used. In the present invention, the polymerizable compound is preferably a compound having an ethylenically unsaturated bond group, for example. As an ethylenic unsaturated bond group, a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

The polymerizable compound may be in any of chemical forms such as monomers, prepolymers, and oligomers, but monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and more preferably 1500 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more.

The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond groups, and one that contains 3 to 6 ethylenically unsaturated bond groups The compound is further preferred. Moreover, it is preferable that the polymerizable compound is a 3-15 functional (meth)acrylate compound, and a 3-6 functional (meth)acrylate compound is more preferable. Specific examples of polymerizable compounds include paragraphs 0095 to 0108 of Japanese Patent Application Publication No. 2009-288705, paragraphs 0227 of Japanese Patent Application Publication No. 2013-029760, and paragraphs 0254 to 0257 of Japanese Patent Application Publication No. 2008-292970. , Japanese Patent Application Publication No. 2013-253224, paragraphs 0034 to 0038, Japanese Patent Application Publication No. 2012-208494, paragraph 0477, Japanese Patent Application Publication No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807 For the compounds described, these contents are incorporated in this specification.

As the polymerizable compound, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol tetraacrylate (as a commercial product is KAYARAD D -320; manufactured by Nippon Kayaku Co., Ltd.), dineopentylene pentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol Alcohol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; manufactured by Shin Nakamura Chemical Co., Ltd.) and these (A A compound having a structure in which a propylene group is bonded via a ethylene glycol and/or propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer Company, Inc.) is preferred. In addition, as the polymerizable compound, diglycerol EO (ethylene oxide) modified (meth)acrylate (M-460 as a commercially available product; manufactured by TOAGOSEI CO., LTD.) and neopentylerythritol can also be used Tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 ( Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 ( TAISEI FINE CHEMICAL CO., LTD.), LIGHT ACRYLATE POB-A0 (KYOEISHA CHEMICAL CO., LTD.), etc.

In addition, as the polymerizable compound, trimethylolpropane tri(meth)acrylate, trimethylolpropane, propylene oxide, and trimethylolpropane, ethylene oxide, are used for modification. Trifunctional (meth)acrylate compounds such as tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate are also preferred. Commercial products of trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M- 306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., Ltd.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A -TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Kayaku Co., Ltd.) etc.

The polymerizable compound can also use a compound having an acid group. By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed. As an acid group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, and a carboxyl group is preferable. Examples of commercially available products of the polymerizable compound having an acid group include ARONIX M-510, M-520, ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), and the like. The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the solubility to the developer is good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production or handling.

It is also preferable that the polymerizable compound is a compound having a caprolactone structure. Polymerizable compounds having a caprolactone structure are commercially available as the KAYARAD DPCA series by Nippon Kayaku Co., Ltd., for example, and include DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

As the polymerizable compound, a polymerizable compound having an alkoxy group can also be used. The polymerizable compound having an alkoxyl group is preferably a polymerizable compound having a vinyloxy group and/or a propyleneoxy group, and a polymerizable compound having a vinyloxy group is more preferred, having 4-20 vinyloxy groups The 3-6 functional (meth)acrylate compounds are more preferred. As a commercially available product of a polymerizable compound having an ethyleneoxy group, for example, SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional (meth)acrylate having 4 ethyleneoxy groups, as a KAYARAD TPA-330, etc., a trifunctional (meth)acrylate of isobutoxy groups.

The polymerizable compound can also be a polymerizable compound having a 茀 skeleton. As commercially available products of the polymerizable compound having a stilbene skeleton, OGSOL EA-0200, EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., a (meth)acrylate monomer having a stilbene skeleton) and the like can be mentioned.

As the polymerizable compound, it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene. As commercially available products of these compounds, KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

As the polymerizable compound, for example, the urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Ester acrylates or ethylene oxide series described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 The urethane compound of the skeleton is also preferred. In addition, a polymerizable compound having an amino group structure or a thioether structure in the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 are used. It is also better. Moreover, as the polymerizable compound, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, and UA-306H can also be used. Commercial products such as 306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by KYOEISHA CHEMICAL CO., LTD.).

The content of the polymerizable compound in the total solid content of the coloring composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and more preferably 40% by mass or less. A polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, the total of these is preferably in the above range.

In addition, from the viewpoints of curability, developability, and film forming properties, the total content of the polymerizable compound and the resin in the total solid content of the coloring composition is preferably 10 to 65% by mass. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. Moreover, it is preferable to contain 30-300 mass parts of resins with respect to 100 mass parts of polymerizable compounds. The lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less.

＜＜Photopolymerization initiator＞＞ The coloring composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a compound having sensitivity to light from the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

As the photopolymerization initiator, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having a diazole skeleton, etc.), phosphine compounds, hexaarylbisimidazoles, oxime compounds, organic peroxides, etc. Oxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyl tris compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an phosphine compound, and a phosphine oxide. Compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium compounds, benzothiazole compounds, diphenyl ketone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl Diazole compounds and 3-aryl substituted coumarin compounds are preferred, and compounds selected from oxime compounds, α-hydroxy ketone compounds, α-amino ketone compounds and phosphine compounds are more preferred, and oxime compounds are Further better. Regarding the photopolymerization initiator, reference can be made to the descriptions in paragraphs 0065 to 0111 of JP 2014-130173 A and Japanese Patent No. 6301489, and this content is incorporated in this specification.

Examples of commercially available products of the α-hydroxy ketone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF Corporation), and the like. Examples of commercially available products of α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF Corporation). As a commercially available product of the phosphine compound, IRGACURE-819, DAROCUR-TPO (above, made by BASF Corporation), etc. are mentioned.

Examples of the oxime compound include the compounds described in JP 2001-233842, the compounds described in JP 2000-080068, the compounds described in JP 2006-342166, and JCS The compound described in Perkin II (1979, pp.1653-1660), the compound described in JCS Perkin II (1979, pp.156-162), Journal of Photopolymer Science and Technology (1995, pp.202) -232) The compound described in JP 2000-066385 A, the compound described in JP 2004-534797 A, and the compound described in JP 2006-342166 A , The compound described in JP 2017-019766 A, the compound described in Japanese Patent No. 6065596, the compound described in International Publication WO2015/152153, and the compound described in International Publication WO2017/051680 The compounds described in JP 2017-198865 A, the compounds described in paragraphs 0025 to 0038 of International Publication WO2017/164127, and the like. Specific examples of the oxime compound include 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxy Aminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzyl Oxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutyl-2-one and 2-ethoxycarbonyloxyimino-1 -Phenylpropan-1-one, etc. Commercial products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF Corporation), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in JP 2012-014052 A). In addition, as the oxime compound, it is also preferable to use a non-coloring compound or a compound with high transparency and not easy to change color. Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (the above are manufactured by ADEKA CORPORATION).

In the present invention, as the photopolymerization initiator, an oxime compound having a sulphur ring can be used. As a specific example of the oxime compound which has a sulphur ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 is mentioned. This content is incorporated into this manual.

In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom can be used. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40, and the compounds described in JP 2014-500852 A The compound (C-3), etc. described in the 2013-164471 Bulletin. This content is incorporated into this manual.

In the present invention, as the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of oxime compounds having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and paragraphs 0070 to 0079 of JP 2014-137466. The compound, the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

In the present invention, as the photopolymerization initiator, an oxime compound having a benzofuran skeleton can be used. As a specific example, OE-01 to OE-75 described in International Publication WO2015/036910 can be cited.

Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.

[化學式6]

[Chemical formula 5]

[Chemical formula 6]

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the oxime compound preferably has a high molar absorption coefficient at a wavelength of 365 nm or a wavelength of 405 nm, more preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method. For example, it is better to use a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use ethyl acetate as a solvent, with a concentration of 0.01 g/L.

As the photopolymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can be used. By using these photo-radical polymerization initiators, two or more radicals are generated from one molecule of the photo-radical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered and the solubility in organic solvents and the like is improved, and it becomes difficult to precipitate over time, and the stability of the coloring composition over time can be improved. As specific examples of the photoradical polymerization initiators having difunctional or trifunctional or higher functions, Japanese Special Publication No. 2010-527339, Japanese Special Publication No. 2011-524436, International Publication WO2015/004565, and Japanese Special Table 2016-532675, paragraphs 0407 to 0412, International Publication WO2017/033680, paragraphs 0039 to 0055, the dimers of oxime compounds, and the compounds described in JP 2013-522445 (E ) And compound (G), Cmpd1-7 described in International Publication WO2016/034963, oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Application No. 2017-523465, Japanese Patent Application Publication No. 2017- The photoinitiator described in paragraphs 0020 to 0033 of 167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP 2017-151342 A, etc.

The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. In the coloring composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof falls within the above-mentioned range.

＜＜Pigment derivatives＞＞ The coloring composition of the present invention can contain a pigment derivative. According to this aspect, the storage stability of the colored composition can be further improved. As the pigment derivative, a compound having a structure in which a part of the pigment is substituted with an acid group, a basic group, a group having a salt structure, or a phthalimine methyl group can be mentioned. As the pigment derivative, a compound represented by formula (B1) is preferred.

式（B1）中，P表示色素結構，L表示單鍵或連接基，X表示酸基、鹼性基、具有鹽結構之基團或酞醯亞胺甲基，m表示1以上的整數，n表示1以上的整數，當m為2以上時複數個L及X可以互不相同，當n為2以上時複數個X可以互不相同。[Chemical formula 7]

In the formula (B1), P represents a pigment structure, L represents a single bond or a linking group, X represents an acid group, a basic group, a group having a salt structure or a phthaliminomethyl group, m represents an integer of 1 or more, and n It represents an integer of 1 or more. When m is 2 or more, the plurality of L and X may be different from each other, and when n is 2 or more, the plurality of X may be different from each other.

Examples of the pigment structure represented by P include pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, dianthraquinone pigment structure, benzisoindole pigment structure, Thiazide indigo pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, two-color pigment structure, perylene pigment structure, perylene pigment structure, benzimidazolone pigment structure , Benzothiazole pigment structure, benzimidazole pigment structure and benzoxazole pigment structure, etc.

Examples of the linking group represented by L include a hydrocarbon group, a heterocyclic group, -NR-, -SO ₂ -, -S-, -O-, -CO-, or a group composed of a combination of these. R represents a hydrogen atom, an alkyl group or an aryl group.

Examples of the acid group represented by X include a carboxyl group, a sulfonic acid group, a carboxylic acid amide group, a sulfonic acid amide group, and an imine acid group. As the carboxylic acid amide group, a group represented by -NHCOR ^X1 is preferred. As the sulfonamide group, a group represented by -NHSO ₂ R ^X2 is preferred. As the imidate group, a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ NHCOR ^X6 is preferred. R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and heterocyclic group represented by R ^X1 to R ^X6 may further have a substituent. As the substituent which may further have, a halogen atom is preferable, and a fluorine atom is more preferable. The basic group represented by X includes an amino group. Examples of the salt structure represented by X include salts of the aforementioned acid groups or basic groups.

As a pigment derivative, the compound of the following structure is mentioned. In addition, Japanese Patent Application Publication No. 56-118462, Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 01-217077, Japanese Patent Application Publication No. 03-009961, Japanese Patent Application Publication No. 03-026767 can also be used. Bulletin, Japanese Patent Application Publication No. 03-153780, Japanese Patent Application Publication No. 03-045662, Japanese Patent Application Publication No. 04-285669, Japanese Patent Application Publication No. 06-145546, Japanese Patent Application Publication No. 06-212088, Japanese Patent Application Publication 06-240158, Japanese Patent Application Publication No. 10-030063, Japanese Patent Application Publication No. 10-195326, International Publication WO2011/024896, paragraphs 0086 to 0098, International Publication WO2012/102399, paragraphs 0063 to 0094, The compounds described in paragraph 0082 of International Publication WO2017/038252 and others are incorporated into this specification. [Chemical formula 8]

The content of the pigment derivative is preferably 1-30 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 15% by mass or less. The pigment derivative may use only 1 type, and may use 2 or more types together. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

＜＜Compounds with cyclic ether groups＞＞ The coloring composition of the present invention can contain a compound having a cyclic ether group. As a cyclic ether group, an epoxy group, an oxetanyl group, etc. are mentioned. The compound having a cyclic ether group is preferably a compound having an epoxy group. Examples of the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups is preferable. The upper limit of the number of epoxy groups may be 100 or less, for example, 10 or less, or 5 or less. As the compound having an epoxy group, paragraphs 0034 to 0036 of Japanese Patent Application Publication No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Application Publication No. 2014-043556, and paragraphs 0085 to of Japanese Patent Application Publication No. 2014-089408 can also be used. The compound described in paragraph 0092 and the compound described in JP 2017-179172 A. These contents are incorporated into this manual.

The compound with epoxy group can be a low molecular compound (for example, less than a molecular weight of 2000, and then less than a molecular weight of 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200-100000, and more preferably 500-50000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and more preferably 3,000 or less.

As the compound having an epoxy group, an epoxy resin can be preferably used. Examples of epoxy resins include epoxy resins which are glycidyl etherifications of phenol compounds, epoxy resins which are glycidyl ethers of various novolac resins, alicyclic epoxy resins, and aliphatic resins. Epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by epoxy propylation of halogenated phenols, with Condensates of epoxy-based silicon compounds and other silicon compounds, copolymers of epoxy-based polymerizable unsaturated compounds and other polymerizable unsaturated compounds, etc. The epoxy equivalent of the epoxy resin is preferably 310-3300g/eq, more preferably 310-1700g/eq, and still more preferably 310-1000g/eq.

Examples of commercially available products of compounds having cyclic ether groups include EHPE3150 (made by Daicel Corporation), EPICLON N-695 (made by DIC CORPORATION), MARPROOF G-0150M, G-0105SA, G-0130SP, and G-0250SP , G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (the above are NOF CORPORATION products, epoxy-containing polymers), etc.

When the coloring composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group in the total solid content of the coloring composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The compound having a cyclic ether group may be only one type or two or more types. In the case of two or more types, it is preferable that the total amount of these is in the above-mentioned range.

＜＜Silane coupling agent＞＞ The coloring composition of the present invention can contain a silane coupling agent. According to this aspect, it is possible to improve the adhesion of the obtained film to the support. In the present invention, the coupling agent refers to a silane compound having a hydrolyzable group and other functional groups. In addition, the hydrolyzable group refers to a substituent that is directly connected to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, as functional groups other than the hydrolyzable group, for example, vinyl, (meth)allyl, (meth)acrylic, mercapto, epoxy, oxetanyl, amino, Urea group, thioether group, isocyanate group, phenyl group, etc., amine group, (meth)acrylic group and epoxy group are preferred. Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP 2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP 2009-242604. Etc. are incorporated into this manual.

The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

＜＜Polymerization inhibitor＞＞ The colored composition of the present invention can contain a polymerization inhibitor. As polymerization inhibitors, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, tertiary butyl catechol, benzoquinone, 4,4'- Thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxyl Amine salt (ammonium salt, cerium salt, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.

＜＜Surface active agent＞＞ The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants can be used. Regarding the surfactant, refer to paragraphs 0238 to 0245 of International Publication No. WO2015/166779, and this content is incorporated in this specification.

In the present invention, the surfactant-based fluorine-based surfactant is preferred. By including a fluorine-based surfactant in the coloring composition, liquid properties (especially, fluidity) can be further improved, and liquid-saving properties can be further improved. In addition, it is also possible to form a film with less uneven thickness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. From the viewpoint of uniformity of the thickness of the coating film and liquid-saving properties, a fluorine-based surfactant having a fluorine content within this range is effective, and the solubility in the colored composition is also good.

Examples of fluorine-based surfactants include those described in paragraphs 0060 to 0064 of Japanese Unexamined Patent Publication No. 2014-041318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014/017669). The surfactants described in paragraphs 0117 to 0132 of the Open Publication No. 2011-132503 are incorporated into this specification. Commercial products of fluorine-based surfactants include, for example, MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (manufactured by DIC Corporation above), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited above), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068 , SC-381, SC-383, S-393, KH-40 (the above are manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (the above are manufactured by OMNOVA SOLUTIONS INC.), etc.

In addition, the fluorine-based surfactant can also suitably use an acrylic compound which has a molecular structure of a functional group containing a fluorine atom, and when heat is applied, the functional group portion containing the fluorine atom is cut and the fluorine atom volatilizes. Examples of such fluorine-based surfactants include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), such as MEGAFACE DS-21 .

Moreover, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. Regarding this type of fluorine-based surfactant, reference can be made to the description in JP 2016-216602 A, which is incorporated into this specification.

上述化合物的重量平均分子量較佳為3000～50000，例如為14000。上述化合物中，表示重複單元的比例之%為莫耳%。Block polymers can also be used for fluorine-based surfactants. For example, the compounds described in JP 2011-089090 A can be cited. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds, which contain repeating units derived from (meth)acrylate compounds having fluorine atoms and those derived from having two or more (preferably) It is a repeating unit of a (meth)acrylate compound of 5 or more) alkoxy groups (preferably ethoxy groups and propoxy groups). The following compounds are also exemplified as fluorine-based surfactants used in the present invention. [Chemical formula 9]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compound, the% representing the proportion of the repeating unit is mole %.

In addition, the fluorine-based surfactant can also use a fluorine-containing polymer having an ethylenically unsaturated bond group in the side chain. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, such as MEGAFACE RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation -72-K etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate). Base compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol two Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901 , 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112 -W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Examples of silicon-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. , Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, KF-6002 (above Shin-Etsu Chemical Co., LTD.), BYK307, BYK323, BYK330 (the above are manufactured by BYK-Chemie Corporation), etc. In addition, a compound having the following structure can also be used as a silicon-based surfactant. [Chemical formula 10]

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

＜＜Ultraviolet absorber＞＞ The colored composition of the present invention can contain an ultraviolet absorber. UV absorbers can use conjugated diene compounds, amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazole compounds, indole compounds, Three 𠯤 compounds and so on. For details of these, please refer to paragraphs 0052 to 0072 of JP 2012-208374, paragraphs 0317 to 0334 of JP 2013-068814, and paragraphs 0061 to 0080 of JP 2016-162946. The contents are incorporated into this manual. As a commercially available product of an ultraviolet absorber, UV-503 (made by DAITO CHEMICAL CO., LTD.) etc. are mentioned, for example. In addition, as the benzotriazole compound, the MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. (Chemical Industry Daily, February 1, 2016) can be cited. In addition, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.

The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

＜＜Antioxidant＞＞ The colored composition of the present invention can contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferable phenol compound, hindered phenol compound can be mentioned. A compound having a substituent at a position (ortho position) adjacent to the phenolic hydroxyl group is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Furthermore, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, phosphorus antioxidants can also be suitably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f] [1,3,2]dioxin-2-yl)oxy]ethyl]amine, bis(2,4-di-tertiarybutyl-6-methylphenol) ethyl phosphite, etc. . Commercial products of antioxidants include, for example, ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO- 80. ADKSTAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used.

The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only 1 type of antioxidant may be used, and 2 or more types may be used. When two or more types are used, the total amount is preferably in the above range.

＜＜Other ingredients＞＞ The coloring composition of the present invention may contain sensitizers, hardening accelerators, fillers, thermal hardening accelerators, plasticizers, and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, etc.) as necessary. Agent, leveling agent, peeling accelerator, fragrance, surface tension regulator, chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. For these ingredients, for example, reference can be made to the description in paragraph 0183 and later of JP 2012-003225 A (corresponding to paragraph 0237 of the specification of U.S. Patent Application Publication No. 2013/0034812), and 0101 to 0104 of JP 2008-250074 A Paragraphs, paragraphs 0107 to 0109, etc., are incorporated into this manual. In addition, the colored composition of the present invention may contain a latent antioxidant as necessary. As a potential antioxidant, the part that functions as an antioxidant is protected by a protective group, which is protected by heating at 100 to 250°C or by heating at 80 to 200°C in the presence of an acid/base catalyst A compound that functions as an antioxidant by detaching its base. Examples of potential antioxidants include compounds described in International Publication WO2014/021023, International Publication WO2017/030005, and Japanese Patent Application Publication No. 2017-008219. As a commercially available product, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like can be mentioned.

Moreover, in order to adjust the refractive index of the obtained film, the coloring composition of this invention may contain a metal oxide. Examples of metal oxides include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , and SiO ₂ . The primary particle size of the metal oxide is preferably from 1 to 100 nm, more preferably from 3 to 70 nm, and most preferably from 5 to 50 nm. The metal oxide may also have a core-shell structure. In this case, the core may also be hollow.

In addition, the colored composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraphs 0036 to 0037 of JP 2017-198787, the compounds described in paragraphs 0029 to 0034 of JP 2017-146350, and JP The compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of 2017-129774, the compounds described in paragraphs 0031 to 0034, and 0058 to 0059 of JP 2017-129674, JP 2017-122803 The compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of the publication, the compounds described in paragraphs 0025 to 0039 of International Publication WO2017/164127, and the compounds described in paragraphs 0034 to 0047 of JP 2017-186546 A The compounds described in paragraphs 0019 to 0041 of Japanese Patent Application Publication No. 2015-025116, the compounds described in paragraphs 0101 to 0125 of Japanese Patent Application Publication No. 2012-145604, and those described in Japanese Patent Application Publication No. 2012-103475 The compounds described in paragraphs 0018 to 0021, the compounds described in paragraphs 0015 to 0018 of JP 2011-257591, the compounds described in paragraphs 0017 to 0021 of JP 2011-191483, and the Japanese patent The compound described in paragraphs 0108 to 0116 of Japanese Patent Application Publication No. 2011-145668, the compound described in paragraphs 0103 to 0153 of Japanese Patent Application Publication No. 2011-253174, and the like.

In the coloring composition of the present invention, the content of free metals that are not bonded or coordinated with pigments, etc. is preferably 100 ppm or less, more preferably 50 ppm or less, more preferably 10 ppm or less, and particularly preferably not containing substantially . According to this aspect, it is possible to stabilize the dispersibility of the pigment (aggregation inhibition), improve the spectroscopic characteristics accompanying the improvement of the dispersibility, stabilize the curable component or suppress the change in conductivity accompanying the elution of metal atoms/metal ions, and improve the display Features etc. In addition, Japanese Patent Application Publication No. 2012-153796, Japanese Patent Application Publication No. 2000-345085, Japanese Patent Application Publication No. 2005-200560, Japanese Patent Application Publication No. 08-043620, Japanese Patent Application Publication No. 2004-145078, Japanese Patent Application Publication No. 2014-119487, Japanese Patent Application Publication No. 2010-083997, Japanese Patent Application Publication No. 2017-090930, Japanese Patent Application Publication No. 2018-025612, Japanese Patent Application Publication No. 2018-025797, Japanese Patent Application Publication No. 2017- The effects described in Bulletin No. 155228, Japanese Patent Application Publication No. 2018-036521, etc. As the types of the above-mentioned free metals, Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt , Cs, Ni, Cd, Pb, Bi, etc. In addition, in the coloring composition of the present invention, the content of free halogen that is not bonded or coordinated with a pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, more preferably 10 ppm or less, and substantially does not contain Especially good. Examples of the halogen include F, Cl, Br, I, and these anions. Examples of methods for reducing free metals or halogens in the coloring composition include washing with ion-exchange water, filtration, ultrafiltration, and purification with ion-exchange resins.

It is also preferable that the coloring composition of the present invention does not contain terephthalate.

For example, when a film is formed by coating, the viscosity (25°C) of the colored composition of the present invention is preferably 1 to 100 mPa·s. The lower limit is more preferably 2 mPa·s or more, and more preferably 3 mPa·s or more. The upper limit is more preferably 50 mPa·s or less, more preferably 30 mPa·s or less, and particularly preferably 15 mPa·s or less.

＜Container Container＞ The storage container of the colored composition of the present invention is not particularly limited, and a known storage container can be used. In addition, as a container, it is also preferable to use a multi-layer bottle with 6 kinds of 6-layer resins constituting the inner wall of the container or a bottle with 6 kinds of resins in a 7-layer structure for the purpose of preventing impurities from mixing into the raw material or coloring composition. . Examples of these containers include those described in JP 2015-123351 A.

＜Method of manufacturing colored composition＞ The colored composition of the present invention can be produced by mixing the aforementioned components. When manufacturing a coloring composition, all components can be dissolved and/or dispersed in an organic solvent at the same time to manufacture a coloring composition, or each component can be appropriately made into two or more solutions or dispersions as needed, and then used At the time (during coating), these are mixed to produce a colored composition.

In addition, when manufacturing the coloring composition, a process including dispersing the pigment is preferable. In the process of dispersing the pigment, as the mechanical force used in the dispersion of the pigment, compression, pressing, impact, shearing, cavitation, etc. can be mentioned. Specific examples of these processes include bead milling, sand milling, roller milling, ball milling, paint agitators, microjets, high-speed impellers, sand mixing, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, in the pulverization of the pigment in the sand mixer (bead mill), it is better to perform the treatment under the condition that the pulverization efficiency is improved by using beads with a small diameter and increasing the filling rate of the beads. Furthermore, it is preferable to remove coarse particles by filtration, centrifugal separation, etc. after the crushing treatment. In addition, the pigment dispersion process and dispersing machine can appropriately use the "Dispersion Technology Encyclopedia, issued by JOHOKIKO CO., LTD., July 15, 2005" or "Suspension (solid/liquid dispersion system)-centered dispersion The actual comprehensive data collection of technology and industrial applications, issued by the Publishing Department of the Management Development Center, October 10, 1978", the manufacturing process and dispersion machine described in paragraph 0022 of the Japanese Patent Publication No. 2015-157893. In addition, in the process of dispersing the pigment, a salt milling step can be used to refine the particles. Regarding the raw materials, equipment, processing conditions, etc. used in the salt milling step, for example, Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629 can be referred to.

When manufacturing a colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign matter and reducing defects. As the filter, as long as it is a filter conventionally used for filtering purposes, etc., it can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (for example, nylon-6, nylon-6, 6), and polyolefin resins such as polyethylene and polypropylene (PP) are used ( Filters containing high-density, ultra-high molecular weight polyolefin resins) and other raw materials. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. As long as the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size of the filter, refer to the nominal value of the filter manufacturer. The filter can use various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (Formerly Nippon micro squirrel Co., Ltd.) and KITZMICROFILTER CORPORATION.

Moreover, it is also preferable to use a fibrous filter material as a filter. As a fibrous filter material, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example. Examples of commercially available products include SBP type series (SBP008, etc.) manufactured by ROKI TECHNO CO., LTD., TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.).

When using filters, different filters can be combined (for example, the first filter and the second filter, etc.). At this time, the filtration in each filter may be performed only once, or may be performed twice or more. In addition, it is also possible to combine filters with different pore sizes within the above range. In addition, the filtration by the first filter is performed only on the dispersion liquid, and it may be filtered by the second filter after mixing other components.

＜Membrane＞ The film of the present invention is a film obtained from the above-mentioned coloring composition of the present invention. The film of the present invention can be used for color filters and the like. Specifically, it can be preferably used as a coloring layer (pixel) of a color filter, and can be more preferably used as a red coloring layer (red pixel) of a color filter. The film thickness of the film of this invention can be adjusted suitably according to the objective. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

＜Color filter＞ Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned film of the present invention. It is more preferable that the pixel as a color filter has the film of the present invention. The color filter of the present invention can be used in solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.

The film thickness of the film of the present invention in the color filter of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

In the color filter of the present invention, the pixel width is preferably 0.5-20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, and more preferably 10.0 μm or less. In addition, the Young's modulus of the pixel is preferably 0.5-20 GPa, and more preferably 2.5-15 GPa.

It is preferable that each pixel included in the color filter of the present invention has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and more preferably 15 nm or less. The lower limit is not specified, but for example, 0.1 nm or more is preferable. The surface roughness of the pixel can be measured using AFM (Atomic Force Microscope) Dimension3100 manufactured by Veeco Instruments Inc., for example. In addition, the contact angle of water on the pixel can be appropriately set to a suitable value, and is typically in the range of 50 to 110°. The contact angle can be measured using a contact angle meter CV-DT·A (manufactured by Kyowa Interface Science Co., LTD.), for example. In addition, the volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω·cm or more, and more preferably 10 ¹¹ Ω·cm or more. The upper limit is not specified, but for example, 10 ¹⁴ Ω·cm or less is preferable. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest Corporation).

Furthermore, in the color filter of the present invention, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxidation resistance, low reflection, hydrophilicity and hydrophobicity, and shielding of light of specific wavelengths (ultraviolet rays, near infrared rays, etc.) can be imparted. As the thickness of the protective layer, 0.01 to 10 μm is preferable, and 0.1 to 5 μm is more preferable. As a method of forming the protective layer, a method of applying a resin composition dissolved in an organic solvent to form it, a chemical vapor deposition method, a method of bonding the molded resin with an adhesive, and the like. Examples of components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polyether resins, polyether sulfide resins, polyphenylene resins, Polyarylene ether phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin , Melamine resin, polyurethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin , Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N _4, etc., can also contain two or more of these components. For example, in the case of a protective layer for the purpose of preventing oxidation, the protective layer preferably contains polyol resin, SiO ₂ , and Si ₂ N ₄ . In addition, in the case of a protective layer for the purpose of low reflection, the protective layer preferably contains (meth)acrylic resin or fluororesin.

When a resin composition is applied to form a protective layer, as a method of applying the resin composition, a known method such as a spin coating method, a casting method, a screen printing method, and an inkjet method can be used. As the organic solvent contained in the resin composition, a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by the chemical vapor deposition method, as the chemical vapor deposition method, a known chemical vapor deposition method (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) can be used ).

The protective layer may contain organic and inorganic fine particles, absorbers with specific wavelengths (for example, ultraviolet rays, near infrared rays, etc.), refractive index modifiers, antioxidants, adhesives, and surfactants as needed. Examples of organic and inorganic particles include, for example, polymer particles (for example, silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, and nitrogen. Titanium, titanium oxynitride, magnesium fluoride, hollow silicon dioxide, silicon dioxide, calcium carbonate, barium sulfate, etc. As the absorber of a specific wavelength, a well-known absorber can be used. Examples of the ultraviolet absorber and the near-infrared absorber include the above-mentioned materials. The content of these additives can be adjusted appropriately, but it is preferably 0.1 to 70% by mass relative to the total mass of the protective layer, and more preferably 1 to 60% by mass.

In addition, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of JP 2017-151176 A can also be used.

The color filter may also have a structure in which pixels (colored layers) of various colors are buried in the area divided by the partition. At this time, the partition system preferably has a low refractive index with respect to each pixel. In addition, the partition wall may be formed by the structure described in US2018/0040656.

<Method of manufacturing color filter> Next, the manufacturing method of the color filter of this invention is demonstrated. The color filter of the present invention can be manufactured through the following steps: a step of forming a coloring composition layer on a support using the above-mentioned coloring composition of the present invention; and a step of patterning the coloring composition layer by photolithography . The pattern formation based on the photolithography method preferably includes the following steps: a step of exposing the colored composition layer into a pattern; and a step of developing and removing the unexposed portion of the colored composition layer to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) can also be provided. The steps are described below.

In the step of forming the colored composition layer, the colored composition of the present invention is used, and the colored composition layer is formed on the support. It does not specifically limit as a support body, According to a use, it can select suitably. For example, a glass substrate, a silicon substrate, etc. can be mentioned, and a silicon substrate is preferable. In addition, charge-coupled devices (CCD), complementary metal oxide semiconductors (CMOS), transparent conductive films, etc. can be formed on the silicon substrate. In addition, sometimes a black matrix is formed on the silicon substrate to isolate each pixel. In addition, an undercoat layer may be provided on the silicon substrate. The undercoat layer is used to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.

As the coating method of the coloring composition, a known method can be adopted. For example, a drop method (drop casting); slit coating method; spray method; roll coating method; spin coating method (spin coating method); cast coating method; slit spin coating method; pre-wet method (For example, the method described in Japanese Patent Application Laid-Open No. 2009-145395); inkjet (for example, on-demand, piezoelectric, thermal), nozzle jet and other jet printing, flexographic printing, screen printing, gravure Various printing methods such as printing, reverse offset printing, metal mask printing, etc.; transfer printing using molds, etc.; nanoimprinting, etc. The application method using inkjet is not particularly limited. For example, "Promotion-Usable inkjet-Unlimited possibilities in patents-Issued in February 2005, SB RESEARCH CO., LTD." Method (especially from pages 115 to 133) and JP 2003-262716, JP 2003-185831, JP 2003-261827, JP 2012-126830, JP 2003-262716 The method described in 2006-169325 Bulletin etc. In addition, regarding the coating method of the coloring composition, refer to the descriptions in International Publication No. WO2017/030174 and International Publication No. WO2017/018419, and these contents are incorporated in this specification.

The colored composition layer formed on the support can be dried (pre-baked). When the film is manufactured by a low-temperature process, pre-baking is not necessary. When pre-baking is performed, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be set to 50°C or higher, for example, or 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, a baking box, etc.

Next, the colored composition layer is exposed in a pattern (exposure step). For example, the colored composition layer can be exposed in a pattern by using a stepper exposure machine, a scanning exposure machine, etc., through a mask having a predetermined mask pattern. Thereby, the exposed part can be hardened.

Examples of radiation (light) that can be used for exposure include g-rays and i-rays. In addition, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and the like. KrF rays (wavelength 248 nm) are preferred. In addition, a light source with a long wavelength of 300 nm or more can also be used.

In addition, at the time of exposure, light may be continuously irradiated for exposure, or pulsed irradiation may be used for exposure (pulse exposure). In addition, pulsed exposure refers to an exposure method in which exposure and pause are repeated in a short period of time (for example, below the millisecond level). In pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but can be set to 1 femtosecond (fs) or more, or can be set to 10 femtoseconds or more. The frequency is preferably above 1 kHz, more preferably above 2 kHz, and even more preferably above 4 kHz. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. The maximum instantaneous illuminance is preferably 50,000,000 W/m ² or more, more preferably 100,000,000 W/m ² or more, and even more preferably 200,000,000 W/m ² or more. In addition, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W/m ² or less, more preferably 800000000 W/m ² or less, and more preferably 500000000 W/m ² or less. In addition, the pulse width refers to the time of irradiating light in the pulse period. In addition, frequency means the number of pulse cycles per second. In addition, the maximum instantaneous illuminance refers to the average illuminance during the pulse period during which light is irradiated. In addition, the pulse period refers to a period in which the irradiation and pause of light in pulse exposure are set to one cycle.

The irradiation amount (exposure amount) is preferably 0.03 to 2.5 J/cm ^{2, and more} preferably 0.05 to 1.0 J/cm ² . Regarding the oxygen concentration during exposure, it can be appropriately selected. In addition to exposure in the atmosphere, for example, it may be in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume or substantially oxygen-free) Exposure can also be performed in a high-oxygen environment with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be appropriately set, and usually can be selected from the range of 1000 W/m ² to 100000 W/m ² (for example, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). The oxygen concentration and the exposure illuminance can be appropriately combined with conditions. For example, it can be set to an oxygen concentration of 10% by volume and an illuminance of 10,000 W/m ² , an oxygen concentration of 35% by volume and an illuminance of 20,000 W/m ² .

Next, the unexposed part of the colored composition layer is developed and removed to form a pattern (pixel). The development and removal of the unexposed part of the colored composition layer can be performed using a developer. Thereby, the coloring composition layer of the unexposed part in the exposure step is eluted in the developing solution, and only the photohardened part remains. The temperature of the developer is preferably 20 to 30°C, for example. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal performance, the step of shaking off the developer solution every 60 seconds and supplying new developer solution can be repeated several times.

Examples of the developer include organic solvents and alkaline developers. As the alkaline developer, an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferred. Examples of alkali agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. , Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline , Pyrrole, piperidine, 1,8-diazebicyclo[5.4.0]-7-undecene and other organic alkaline compounds or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, partial Inorganic alkaline compounds such as sodium silicate. Regarding the alkaline agent, a compound with a large molecular weight is preferable in terms of environment and safety. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. In addition, the developer may also contain a surfactant. As the surfactant, the above-mentioned surfactants can be mentioned, and nonionic surfactants are preferred. From the viewpoint of convenient transportation or storage, the developer can be temporarily made into a concentrated solution and diluted to the required concentration during use. The dilution ratio is not particularly limited, and can be set in the range of 1.5 to 100 times, for example. Furthermore, it is also preferable to rinse (rinse) with pure water after development. Moreover, as for the rinsing, it is preferable to perform the rinsing by rotating the support on which the coloring composition layer after development is formed, and supplying a rinsing liquid to the coloring composition layer after development. Moreover, it is also preferable to perform it by moving the nozzle which sprays a rinse liquid from the center part of a support body to the peripheral part of a support body. At this time, when moving from the center portion of the support body of the nozzle to the peripheral edge portion, the nozzle can be moved while gradually reducing the movement speed of the nozzle. By performing rinsing in this way, the in-plane deviation of rinsing can be suppressed. In addition, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center of the support to the peripheral edge.

After development, it is also preferable to perform additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure treatment and post-baking are curing treatments after development for complete curing. The heating temperature during post-baking is preferably 100 to 240°C, and more preferably 200 to 240°C. The post-baking can be performed continuously or intermittently using heating mechanisms such as a heating plate, a convection oven (hot air circulating dryer), and a high-frequency heater so as to meet the above-mentioned conditions. When performing additional exposure processing, the light used for exposure is preferably light with a wavelength of 400 nm or less. In addition, the additional exposure process can be performed by the method described in KR1020170122130A.

＜Solid-state imaging device＞ The solid-state imaging element of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging element of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state imaging element. For example, the following structures can be mentioned.

It has the following structure: on a substrate, there are a plurality of photodiodes and polysilicon that constitute the light receiving area of a solid-state image sensor (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) The transmission electrode is composed of a light-shielding film that only opens the light-receiving part of the photodiode on the photodiode and the transmission electrode, and the light-shielding film has nitrogen formed to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode The device protective film composed of silicide, etc. has a color filter on the device protective film. Furthermore, it may be a configuration with a light-concentrating mechanism (for example, a micro lens, etc., the same below) on the device protective film and under the color filter (close to one side of the substrate), or a light-focusing mechanism on the color filter The composition and so on. In addition, the color filter may have a structure in which each colored pixel is buried in a space separated by a partition wall, for example, in a grid shape. It is preferable that the partition system at this time has a low refractive index with respect to each colored pixel. Examples of imaging devices having such structures include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. WO2018/043654. The imaging device equipped with the solid-state imaging element of the present invention can be used in vehicle cameras or surveillance cameras in addition to digital cameras or electronic devices with imaging functions (mobile phones, etc.).

＜Image display device＞ The image display device of the present invention has the above-mentioned film of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. The definition of image display devices and the details of each image display device are described in, for example, "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)" and "Display Devices (Junaki Ibuki) Published by Sanyo Tosho Publishing Co., Ltd. in 1989)” etc. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, issued by the Industrial Research Council, 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology". [Example]

Hereinafter, the present invention will be described in further detail with examples. The materials, usage amounts, ratios, processing content, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

＜Measurement of resin weight average molecular weight (Mw)) The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) under the following conditions. Types of columns: connecting TOSOH TSKgel Super HZM-H､TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 columns Developing solvent: tetrahydrofuran Column temperature: 40℃ Flow rate (sample injection volume): 1.0μL (sample concentration: 0.1% by mass) Device name: HLC-8220GPC manufactured by TOSOH Corporation Detector: RI (refractive index) detector Calibration curve base resin: polystyrene resin

<Measurement of the length of the minor axis and the length of the major axis of the pigment> Use a scanning electron microscope to digitize the image obtained by shooting at an acceleration voltage of 5kV and an imaging magnification of 100,000 times to create image brightness data in the long axis direction and the short axis direction of the pigment (coordinates from the long axis direction) , The coordinates of the minor axis and the brightness are composed of three components.). In digitization, the image is divided into 1280 in the width direction and processed with 8 bits of brightness to obtain 256 gray-scale data, and the image brightness of each divided coordinate point is converted into a predetermined gray-scale value. Next, in the obtained image brightness data, the coordinates of the direction corresponding to the long axis of the particle are set as the horizontal axis, and the average value of the brightness at each coordinate point in the long axis direction (that is, divided into 1280) The average value of the brightness in the coordinate points) was set on the vertical axis to create a brightness curve. Differentiate the produced brightness curve to produce a differential curve, and determine the coordinates of the paint boundary from the peak position of the produced differential curve. Repeat the operation of setting the coordinates in the direction corresponding to the long axis of the paint as the horizontal axis 3 times, and set the longest axis length as the long axis length. Repeat the operation of setting the coordinates as the horizontal axis 3 times in the minor axis direction, and set the shortest axis length as the minor axis length. Specifically, the length of the major axis refers to the length of an axis (straight line) that can take the length of the longest particle as the major axis. On the other hand, the short axis refers to an axis determined to be the longest length when the particle length is taken on a straight line orthogonal to the long axis, and the length of this axis is defined as the short axis length. In addition, the arithmetic average of the minor axis length and the major axis length of 100 pigments was calculated, and the average of the minor axis length of the pigment and the average of the major axis length of the pigment were calculated.

分散劑D1：下述結構的樹脂（Mw=24000、在主鏈上標記之數值為莫耳比，在側鏈上標記之數值為重複單元的數量。） [化學式12]

<Preparation of pigment dispersion> (Pigment dispersion A1-1～A1-7) 9 parts by mass of CI Pigment Green 58, 6 parts by mass of CI Pigment Yellow 185, 2.5 parts by mass of pigment derivative Y1, dispersant A mixture of 5 parts by mass of D1 and 77.5 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 230 parts by mass of zirconia beads with a diameter of 0.3 mm are added, and after dispersion treatment with a paint stirrer, it is filtered The beads were separated, thereby preparing pigment dispersion liquids 1-1 to A1-7. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In addition, by changing the dispersion time, the major axis length and minor axis length of the pigment 1 and the pigment 2 were adjusted to be the values described in the following table, respectively. In these pigment dispersions, the solid content concentration is 22.5% by mass, and the pigment content is 15% by mass. Pigment derivative Y1: a compound having the following structure. [Chemical formula 11]

Dispersant D1: Resin with the following structure (Mw=24000, the value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units.) [Chemical formula 12]

(Pigment dispersion A2-1～A2-7) To a mixture of 9 parts by mass of CI Pigment Green 36, 6 parts by mass of CI Pigment Yellow 150, 2.5 parts by mass of pigment derivative Y1, 5 parts by mass of dispersant D1 and 77.5 parts by mass of PGMEA, add diameter 230 parts by mass of 0.3 mm zirconia beads were dispersed using a paint stirrer, and then the beads were separated by filtration to prepare pigment dispersions A2-1 to A2-7. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In addition, by changing the dispersion time, the major axis length and minor axis length of the pigment 1 and the pigment 2 were adjusted to be the values described in the following table, respectively. In these pigment dispersions, the solid content concentration is 22.5% by mass, and the pigment content is 15% by mass.

(Pigment dispersion A3) To a mixture of 9 parts by mass of CI Pigment Green 58, 6 parts by mass of CI Pigment Yellow 139, 2.5 parts by mass of pigment derivative Y1, 5 parts by mass of dispersant D1 and 77.5 parts by mass of PGMEA, add diameter After 230 parts by mass of 0.3 mm zirconia beads were dispersed using a paint stirrer, the beads were separated by filtration to prepare a pigment dispersion liquid A3. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In this pigment dispersion, the solid content concentration was 22.5% by mass, and the pigment content was 15% by mass.

(Pigment dispersion A4) To a mixture of 10.5 parts by mass of CI Pigment Red 254, 4.5 parts by mass of CI Pigment Yellow 139, 2.0 parts by mass of pigment derivative Y1, 5.5 parts by mass of dispersant D1 and 77.5 parts by mass of PGMEA, add diameter 230 parts by mass of 0.3 mm zirconia beads were dispersed using a paint stirrer, and then the beads were separated by filtration to prepare a pigment dispersion liquid A4. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In this pigment dispersion, the solid content concentration was 22.5% by mass, and the pigment content was 15% by mass.

分散劑D2：下述結構的化合物 [化學式14]

(Pigment dispersion A5-1, A5-2) 10.5 parts by mass of CI Pigment Red 177, 4.5 parts by mass of CI Pigment Yellow 139, 2.0 parts by mass of pigment derivative Y2, 5.5 parts by mass of dispersant D2, and PGMEA After adding 230 parts by mass of zirconia beads with a diameter of 0.3mm to a mixture of 77.5 parts by mass of the mixture, using a paint stirrer for dispersion treatment, the beads were separated by filtration to prepare pigment dispersions A5-1 and A5-2 . The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In addition, by changing the dispersion time, the long axis length and the short axis length of the pigment 1 and the pigment 2 were adjusted to the values described in the following table, respectively. In these pigment dispersions, the solid content concentration is 22.5% by mass, and the pigment content is 15% by mass. Pigment derivative Y2: a compound of the following structure [Chemical formula 13]

Dispersant D2: Compound of the following structure [Chemical formula 14]

(Pigment dispersion A6) To a mixture of 10.5 parts by mass of CI Pigment Red 264, 4.5 parts by mass of CI Pigment Yellow 139, 2.0 parts by mass of pigment derivative Y1, 5.5 parts by mass of dispersant D1, and 77.5 parts by mass of PGMEA, add diameter After 230 parts by mass of 0.3 mm zirconia beads were dispersed using a paint stirrer, the beads were separated by filtration to prepare a pigment dispersion liquid A6. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In this pigment dispersion, the solid content concentration was 22.5% by mass, and the pigment content was 15% by mass.

(Pigment dispersion A7) To a mixture of 10.5 parts by mass of CI Pigment Red 272, 4.5 parts by mass of CI Pigment Yellow 139, 2.0 parts by mass of pigment derivative Y1, 5.5 parts by mass of dispersant D1 and 77.5 parts by mass of PGMEA, add diameter 230 parts by mass of 0.3 mm zirconia beads were subjected to dispersion treatment using a paint stirrer, and then the beads were separated by filtration to prepare a pigment dispersion liquid A7. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In this pigment dispersion, the solid content concentration was 22.5% by mass, and the pigment content was 15% by mass.

(Pigment dispersion A8) 10.5 parts by mass of red pigment 1, 4.5 parts by mass of CI Pigment Yellow 139, 2.0 parts by mass of pigment derivative Y1, 5.5 parts by mass of dispersant D1, and 77.5 parts by mass of PGMEA To the mixed solution, 230 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and after dispersion treatment using a paint stirrer, the beads were separated by filtration to prepare a pigment dispersion liquid A8. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In this pigment dispersion, the solid content concentration was 22.5% by mass, and the pigment content was 15% by mass. Red pigment 1: A compound of the following structure [Chemical formula 15]

(Pigment dispersion A9-1, A9-2) A mixture of 12 parts by mass of CI Pigment Blue 15:6, 3 parts by mass of CI Pigment Violet 23, 2.7 parts by mass of pigment derivative Y1, 4.8 parts by mass of dispersant D1, and 77.5 parts by mass of PGMEA, 230 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and after performing dispersion treatment using a paint stirrer, the beads were separated by filtration to prepare pigment dispersions A9-1 and A9-2. The long axis length and the short axis length of the pigment 1 and the pigment 2 contained in the pigment dispersion liquid are the values in the following table, respectively. In addition, by changing the dispersion time, the major axis length and minor axis length of the pigment 1 and the pigment 2 were adjusted to be the values described in the following table, respectively. In these pigment dispersions, the solid content concentration is 22.5% by mass, and the pigment content is 15% by mass.

(Pigment dispersion A10) To mix 12 parts by mass of CI Pigment Blue 15:6, 3 parts by mass of V dye 1, 2.7 parts by mass of pigment derivative Y1, and 4.8 parts of dispersant D1 as described in paragraph 0292 of JP 2015-041058 A A mixture of parts by mass and 77.5 parts by mass of PGMEA was added to 230 parts by mass of zirconia beads with a diameter of 0.3 mm, and after dispersion treatment using a paint stirrer, the beads were separated by filtration to prepare pigment dispersion A10. The long axis length and the short axis length of the pigment 1 contained in the pigment dispersion liquid are the values in the following table, respectively. In this pigment dispersion, the solid content concentration was 22.5% by mass, and the color material content (the total amount of the pigment and the dye) was 15% by mass.

[Table 1]

The abbreviations in the above table are as follows. PG36: C.I. Pigment Green 36 PG58: C.I. Pigment Green 58 PR254: C.I. Pigment Red 254 PR264: C.I. Pigment Red 264 PR272: C.I. Pigment Red 272 Red pigment 1: The compound of the above structure PR177: C.I. Pigment Red 177 PB15:6: C.I. Pigment Blue 15:6 PY185: C.I. Pigment Yellow 185 PY150: C.I. Pigment Yellow 150 PY139: C.I. Pigment Yellow 139 PV23: C.I. Pigment Violet 23

<Preparation of coloring composition> After mixing the raw materials described in the following table, it was filtered using a nylon filter (manufactured by NIHON PALL Corporation) with a pore size of 0.45 μm to prepare a coloring composition. Compositions 101 to 118 and C101 to C103 are green coloring compositions, compositions 201 to 205 and C201 are red coloring compositions, and compositions 301, 302, and C301 are blue coloring compositions.

[Table 2]

[table 3]

[Table 4]

The raw materials described in the above table are as follows.

(Pigment dispersion) Pigment dispersion A1-1～A1-7, A2-1～A2-7, A3, A4, A5-1, A5-2, A6, A7, A8, A9-1, A9-2, A10: the above-mentioned pigments Dispersion liquid A1-1～A1-7, A2-1～A2-7, A3, A4, A5-1, A5-2, A6, A7, A8, A9-1, A9-2, A10

(Resin) B1: Resin with the following structure (the value marked on the main chain is molar ratio. Mw: 10,000, acid value: 70 mgKOH/g, C=C value: 1.4 mmol/g) [Chemical formula 16]

(Polymerizable monomer) M1: OGSOL EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., a (meth)acrylate monomer having a stilbene skeleton, C=C value: 2.1 mmol/g) M2: the following Structure compound (C=C value: 10.4mmol/g) [Chemical formula 17]

(Initiator) I1, I3, I5: Compounds of the following structure [Chemical formula 18]

(Surfactant) W1: Compound of the following structure [Chemical formula 19]

(Additive) T1: EHPE3150 (made by Daicel Corporation, epoxy resin) T2: Compound of the following structure (silane coupling agent) [Chemical formula 20]

<Evaluation of film shrinkage> CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was coated on a glass substrate by spin coating so that the film thickness became 0.1 μm, and heated at 220°C using a hot plate The base layer was formed by heating for 1 hour. The film thickness after baking later becomes the film thickness described in the following table. The coloring composition is coated on the glass substrate with a base layer by a spin coating method. Heated at ℃ for 2 minutes. Next, an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) was used to irradiate the entire surface of the glass substrate with i-rays at an exposure amount of 1000 mJ/cm ² through a mask of an open frame to perform exposure. Then, it heated at 200 degreeC for 5 minutes using the hotplate, and formed the film. The film thickness of the obtained film was measured using a palpation profile analysis system DektakXT (manufactured by BRUKER CORPORATION). Next, the film produced above was left to stand for 100 hours at a temperature of 110°C and a humidity of 85% at a constant temperature and humidity. The film thickness of the film after the moisture resistance test was measured, the shrinkage rate of the film was measured according to the following formula, and the film shrinkage was evaluated by the following criteria. Regarding the film thickness of the film, each film before and after the moisture resistance test was measured at five equal positions along the diameter direction of the glass substrate, and the average value was used. Film shrinkage (%)={(film thickness of the film before the humidity resistance test-film thickness of the film after the humidity resistance test)/film thickness of the film before the humidity test}×100 (evaluation criteria) A: Film The shrinkage rate is less than 5% B: The film shrinkage rate is 5% or more and less than 10% C: The film shrinkage rate is 10% or more and less than 20% D: The film shrinkage rate is 20% or more

＜Evaluation of color value＞ The colored composition described in the following table was coated on the glass substrate by the spin coating method. Then, it heated at 100 degreeC for 2 minutes using a hotplate, and formed the film with the film thickness shown in the following table. The obtained film was incident with light of the wavelengths described in the following table, and the transmittance was measured with a spectrometer (UV4100, manufactured by Hitachi High-Technologies Corporation), and the optical density (OD value) was measured. The obtained optical density was normalized by the film thickness, thereby obtaining the relative value of the color value. In addition, with regard to the film formed using the green coloring composition, light with a wavelength of 660 nm was incident. In addition, with regard to the film formed using the red coloring composition, light with a wavelength of 530 nm was incident. In addition, with regard to the film formed using the blue coloring composition, light with a wavelength of 610 nm was incident.

<Evaluation of pattern formation and residue> CT-4000L (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to 8 inches (20.32) using a spin coater so that the thickness became 0.1 μm after post-baking cm) On a silicon wafer, use a heating plate to heat at 220°C for 300 seconds to form a primer layer, thereby obtaining a silicon wafer with a primer layer. Next, the film thickness after baking later became the film thickness described in the following table, and each coloring composition was apply|coated by the spin coating method. Next, a hot plate was used for post-baking at 100°C for 2 minutes. Next, using the i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), the mask with a Bayer pattern formed by a pixel (pattern) size of 1 μm square was performed by i-ray at an exposure amount of 200 mJ/cm ² The exposure. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23°C for 60 seconds. Then, it is rinsed with a rotating spray, and further rinsed with pure water. Next, heating was performed at 200° C. for 5 minutes using a hot plate, thereby forming pixels (patterns).

(Evaluation method of pattern formation) Using a high resolution FEB (Field Emission Beam) length measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Technologies Corporation), the image portion (pattern) of the obtained pixels was observed. A: A pattern with a target line width is formed without deformation, and the difference between the line width at the center of the pattern and the line width at the end is less than 5%. B: A pattern with an approximate target line width is formed, but the difference between the line width at the center of the pattern and the line width at the ends is 5% or more and less than 10%. C: A pattern with an approximate target line width is formed, but the difference between the line width at the center of the pattern and the line width at the ends is 10% or more and less than 30%. D: Except for A to C or pattern formation.

(Evaluation method of residue) A high-resolution FEB (Field Emission Beam) length measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Technologies Corporation) was used to observe the residues in the non-image area (between pixels) of the obtained pixels. A: No residue can be seen at all. B: A residue is seen in an area exceeding 0% and less than 5% of the non-image area. C: A residue is seen in an area of 5% or more and less than 10% of the non-image area. D: A residue is seen in 10% or more of the non-image area.

[table 5]

[Table 6]

[Table 7]

As shown in the above table, all the examples using the compositions 101 to 118, 201 to 205, 301, and 302 can form a film that suppresses film shrinkage. Furthermore, the evaluation of pattern formability and residue was also good. In addition, as can be seen from the results of Examples 101 and 107 to 111 and the results of Test Examples 112 to 117, the use of pigments with a major axis length/minor axis length value of 1.4 or more and 3.0 or less can produce higher color values.的膜。 The film.

(Experimental example 1001) After the film thickness after baking becomes 1.0 μm, the Green composition is coated on the silicon wafer by the spin coating method. Next, using a hot plate, it heated at 100 degreeC for 2 minutes. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm was exposed at an exposure amount of 1000 mJ/cm ² through a mask of a 2 μm square dot pattern. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23°C for 60 seconds. Then, it is rinsed with a rotating spray, and further rinsed with pure water. Then, the Green composition was patterned by heating (post-baking) at 200°C for 5 minutes using a hot plate. The Red composition and the Blue composition were sequentially patterned in the same way to form red, green and blue colored patterns (Bayer patterns). As the Green composition, composition 101 was used. As the Red composition, composition 201 was used. As the Blue composition, composition 301 was used. In addition, the Bayer pattern is as disclosed in the specification of U.S. Patent No. 3,971,065. The color filter element with one red element, two green elements and one blue element is repeated. 2×2 array pattern. The obtained color filter is assembled on the solid-state imaging element according to a known method. The solid-state imaging element has better image recognition capabilities.

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Claims (18)

A coloring composition comprising a colorant, a resin and an organic solvent, wherein: The coloring composition contains 50% by mass or more of the coloring agent in the total solid content, This coloring agent contains 40 mass% or more of pigment A whose ratio of the minor axis length to the major axis length, that is, the value of the major axis length/minor axis length is 1.4 or more. The colored composition as described in item 1 of the scope of patent application, wherein The coloring agent contains 60% by mass or more in the total solid content of the coloring composition. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein The value of the major axis length/minor axis length of the pigment A is 1.4 or more and 3.0 or less. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein The average length of the major axis of the pigment A is 15 nm to 150 nm. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein The average value of the minor axis length of the pigment A is 10 nm to 100 nm. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein The pigment A is a red pigment. The coloring composition as described in item 6 of the scope of patent application, wherein The red pigment is at least one selected from the group consisting of Color Index Pigment Red 254, Color Index Pigment Red 264 and Color Index Pigment Red 272. The coloring composition described in item 1 or item 2 of the scope of the patent application includes a photopolymerization initiator and a polymerizable compound. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein The resin contains an alkali-soluble resin. The coloring composition described in item 1 or item 2 of the scope of patent application is used to form patterns by photolithography. The coloring composition described in item 1 or item 2 of the scope of patent application is used in solid-state imaging devices. The coloring composition described in item 1 or item 2 of the scope of patent application is used for color filters. The coloring composition described in item 12 of the scope of patent application is used to form red pixels. A film obtained from the colored composition described in any one of items 1 to 13 in the scope of patent application. A manufacturing method of a color filter, which has: The step of using the coloring composition described in any one of items 1 to 13 of the scope of patent application to form a coloring composition layer on the support; and The step of patterning the colored composition layer by photolithography. A color filter having the film described in item 14 of the scope of patent application. A solid-state imaging element having the film described in item 14 of the scope of patent application. An image display device having the film described in item 14 of the scope of patent application.