JP7284184B2 - Coloring composition, film, method for producing color filter, color filter, solid-state imaging device, and image display device - Google Patents

Description

The present invention relates to coloring compositions containing pigments. The present invention also relates to a film using the coloring composition, a method for producing a color filter, a color filter, a solid-state imaging device, and an image display device.

2. Description of the Related Art In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements. A color filter is manufactured using a coloring composition containing a coloring agent such as a pigment.

In Patent Document 1, a pigment and a binder component are contained as essential components, and the content of primary particles that satisfy the formula (1) is 70 when the minor axis of the primary particles of the pigment is a and the major axis is b. Forming colored pixels of a color filter using an image-forming coloring composition having a shape distribution in which the content of primary particles satisfying the formula (2) is 5% by volume or less at 5% by volume or more. is described.
b/a<1.4 (1)
b/a≧1.8 (2)

On the other hand, Patent Document 2 discloses an invention relating to a pigment ink composition used for ink for inkjet printers and the like, which contains pigment particles containing at least needle-like pigment particles, a dispersant, and a solvent, and comprises needle-like pigment particles. has a needle-like shape with an aspect ratio of 3 or more, an average aspect ratio of 5 or more and 7 or less, an average minor axis of 20 nm or more and 30 nm or less, and a distribution of the minor axis standard deviation of 2.0 nm or less, and An invention has been described that relates to a pigment ink composition in which needle-like pigment particles are coated with a dispersant.

JP-A-10-239835 JP 2009-221266 A

According to the studies of the present inventors, it was found that a film formed using a coloring composition containing a pigment tends to undergo film shrinkage. It was found that film shrinkage tends to occur particularly in environments with high humidity.

When film shrinkage occurs, voids are likely to occur between adjacent members. For example, when pixels of a color filter are formed using a coloring composition containing a pigment, when the pixels shrink and the line width of the pixels decreases, voids are generated between adjacent pixels and the sensitivity of the device changes. Sometimes I end up

Accordingly, an object of the present invention is to provide a coloring composition capable of forming a film with suppressed film shrinkage. Another object of the present invention is to provide a film using this coloring composition, a method for producing a color filter, a color filter, a solid-state imaging device, and an image display device.

According to the study of the present inventors, the present inventors have found that the above objects can be achieved with the following configuration, and have completed the present invention. Accordingly, the present invention provides the following.
<1> A coloring composition containing a coloring agent, a resin and an organic solvent,
Containing 50% by mass or more of the coloring agent in the total solid content of the coloring composition,
The coloring composition contains 40% by mass or more of a pigment A having a long axis length/short axis length ratio of 1.4 or more.
<2> The coloring composition according to <1>, which contains 60% by mass or more of the coloring agent in the total solid content of the coloring composition.
<3> The colored composition according to <1> or <2>, wherein the pigment A has a major axis length/minor axis length value of 1.4 or more and 3.0 or less.
<4> The colored composition according to any one of <1> to <3>, wherein the pigment A has an average long axis length of 15 to 150 nm.
<5> The colored composition according to any one of <1> to <4>, wherein the pigment A has an average minor axis length of 10 to 100 nm.
<6> The colored composition according to any one of <1> to <5>, wherein the pigment A is a red pigment.
<7> The coloring composition according to <6>, wherein the red pigment is at least one selected from 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>, comprising a photopolymerization initiator and a polymerizable compound.
<9> The colored composition according to any one of <1> to <8>, wherein the resin comprises an alkali-soluble resin.
<10> The colored composition according to any one of <1> to <9>, which is for pattern formation by photolithography.
<11> The colored composition according to any one of <1> to <10>, which is for a solid-state imaging device.
<12> The colored composition according to any one of <1> to <10>, which is used for color filters.
<13> The coloring composition according to <12>, which is for forming red pixels.
<14> A film obtained from the colored composition according to any one of <1> to <13>.
<15> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <13>, and patterning the colored composition layer by a photolithography method A method for manufacturing a color filter comprising:
<16> A color filter having the film according to <14>.
<17> A solid-state imaging device comprising the film according to <14>.
<18> An image display device comprising the film according to <14>.

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

The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, a pigment means a compound that is difficult to dissolve in a solvent. For example, the pigment preferably has a solubility of 0.1 g or less, more preferably 0.01 g or less, in 100 g of water at 23°C and 100 g of propylene glycol monomethyl ether acetate at 23°C.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .

<Coloring composition>
The coloring composition of the present invention is a coloring composition containing a coloring agent, a resin and an organic solvent,
Containing 50% by mass or more of the coloring agent in the total solid content of the coloring composition,
The colorant is characterized by containing 40% by mass or more of Pigment A having a ratio of major axis length to minor axis length of 1.4 or more.

According to the coloring composition of the present invention, shrinkage of the obtained film can be suppressed by containing 50% by mass or more of the coloring agent containing 40% by mass or more of the above-described pigment A in the total solid content of the coloring composition. It is presumed that the pigment A was densely spread in the obtained film, and as a result, the shrinkage of the obtained film was suppressed. In particular, film shrinkage can be effectively suppressed even when the film is exposed to an environment of high humidity for a long time. In addition, since the coloring composition of the present invention contains a coloring agent in an amount of 50% by mass or more, a film having a high color value can be formed. Therefore, it is possible to achieve thinning while maintaining desired spectral characteristics.

In the present invention, the value of long axis length/short axis length of Pigment A is preferably 1.4 or more and 3.0 or less. According to this aspect, when a pattern is formed by photolithography using the coloring composition of the present invention, it is possible to suppress the occurrence of development residuals and form a pattern with good rectangularity.

In the present invention, Pigment A is preferably a red pigment. Red pigments generally tend to have a low color value. It can be spread densely and can form a film with a high red color value.

The coloring composition of the present invention can be preferably used as a coloring composition for solid-state imaging devices. Moreover, the coloring composition of this invention can be preferably used as a coloring composition for color filters. Specifically, it can be preferably used as a coloring composition for forming pixels of a color filter, and more preferably used as a coloring composition for forming pixels of a color filter used in a solid-state imaging device. Color filter pixels 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 is preferably used as a coloring composition for forming red pixels.

The colored composition of the present invention can be preferably used for pattern formation in photolithography. In this case, the colored composition of the present invention preferably contains a photopolymerization initiator and a polymerizable compound. Further, the resin contained in the coloring composition preferably contains an alkali-soluble resin.

The colored composition of the present invention can also be used as a composition for forming colored microlenses. Examples of a method for manufacturing a color microlens include the method described in Japanese Patent Application Laid-Open No. 2018-010162.

Each component used in the coloring composition of the present invention is described below.

<<coloring agent>>
The coloring composition of the present invention contains a coloring agent. Colorants include chromatic colorants such as red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. Colorants include pigments and dyes, and those containing pigments are used. The pigment may be either an inorganic pigment or an organic pigment. As the pigment, an inorganic pigment or a material in which a part of an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.

The colorant used in the present invention is 40 masses of pigment A (hereinafter also simply referred to as pigment A) having a value of long axis length/short axis length, which is the ratio of short axis length to long axis length, of 1.4 or more. % or more. The value of long axis length/short axis length of Pigment A is preferably 1.4 or more and 3.0 or less. If the value of the long axis length/short axis length of the pigment A is within the above range, it is easy to obtain a film with a high color value and suppressed film shrinkage. Furthermore, when a pattern is formed by photolithography using the coloring composition of the present invention, it is possible to suppress the occurrence of development residuals and form a pattern with good rectangularity.

The upper limit of the long axis length/short axis length of Pigment A is preferably 2.7 or less, and 2.4 or less, for the reason that light scattering is suppressed and a film with high brightness is easily obtained. is more preferable. Further, the lower limit of the long axis length/short axis length of the pigment A is preferably 1.6 or more, more preferably 1.8 or more, for the reason that the pigment can be more densely spread in the film. is more preferable, and 2.0 or more is more preferable.

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

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

In this specification, the long axis length and the short axis length are values measured by the following method. That is, using a scanning electron microscope, an image taken at an acceleration voltage of 5 kV and an imaging magnification of 100,000 times is digitized, and image brightness data in the long axis direction and short axis direction of the particle (coordinates in the long axis direction, short axis direction , and three components of luminance). In digitization, an image is divided into 1280 in the width direction, processed with 8-bit luminance to obtain data of 256 gradations, and the image luminance of each divided coordinate point is converted into a predetermined gradation value. Next, in the obtained image brightness data, the coordinate in the direction corresponding to the long axis of the particle is taken as the horizontal axis, and the average value of brightness at each coordinate point in the long axis direction (that is, the average value of brightness at each coordinate point divided by 1280) ) on the vertical axis to create a luminance curve. The created brightness curve is differentiated to create a differential curve, and the coordinates of the particle boundary are specified from the peak position of the created differential curve. The operation of taking the coordinate corresponding to the major axis of the particle as the horizontal axis is repeated three times, and the longest axis length is taken as the major axis length. The operation of taking the coordinates along the horizontal axis is repeated three times in the short axis direction, and the shortest axis length is taken as the short axis length. Specifically, the length of the major axis is defined as the axis (straight line) that allows the longest particle length to be determined as the major axis. On the other hand, the minor axis is determined as the longest axis when the particle length is taken by a straight line orthogonal to the major axis, and this axis length is defined as the minor axis length.

Further, the average short axis length of pigment A and the average long axis length of pigment A are the arithmetic average values of the short axis length and long axis length of 100 pigments A, respectively.

As a method for adjusting the long axis length/short axis length value of the pigment, there is a method of adjusting the long axis length/short axis length value by adjusting the milling conditions of the pigment, and the type and amount of the particle growth inhibitor is adjusted. Examples include a method of adjusting the values of major axis length/minor axis length by adjusting and milling, and a method of adjusting the value of major axis length/minor axis length by heating and aging the pigment. Examples of grain growth inhibitors include compounds described in paragraphs 0041 to 0050 of JP-A-2009-221266.

The types of pigments used in the present invention include those shown below.

Color Index (C.I.) 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), etc. (above, yellow pigment)
C. I. 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. (above, orange pigment),
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), 61 (xanthene), etc. (purple pigments),
C. I. 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), 88 (methine/polymethine system), etc. (above, blue pigment),
C. I. 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 (xanthene, Organo Ultramarine, Bluish Red), etc. (the above are red pigments).

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used. Specific examples include compounds described in International Publication WO2015/118720. Further, as a green pigment, a compound described in CN106909027A, a phthalocyanine compound having a phosphoric acid ester as a ligand, and the like can also be used.

An aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

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

Further, as a yellow pigment, the compound described in JP-A-2018-62644 can also be used. This compound can also be used as a pigment derivative.

Further, as a red pigment, a diketopyrrolopyrrole pigment having at least one bromine atom substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 A pyrrole pigment or the like can also be used. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.

Pigment A used in the present invention preferably contains a red pigment. Also, the red pigment is preferably a diketopyrrolopyrrole compound. The red pigment is preferably at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272, more preferably Color Index Pigment Red 272. Red pigments generally tend to have a low color value, but by using a red pigment having a long axis length/short axis length value of 1.4 or more, a film with a high red color value can be obtained. can be formed.

In the present invention, a dye can also be used as the coloring agent. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used. Further, thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can also be preferably used. Further, as the yellow dye, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraph numbers 0013-0058 of JP-A-2014-026228, and the like can also be used.

In the present invention, a pigment multimer can also be used as the coloring agent. The dye multimer is preferably a dye that is dissolved in a solvent and used, but the dye multimer may form particles, and when the dye multimer is particles, it is usually dispersed in the solvent. Used. The particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682. A 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 may be 100 or less. A plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, and International Publication WO2016/031442. Compounds can also be used.

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

The coloring agent used in the coloring composition of the present invention has a pigment content of 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. is more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit can be 100% by mass. Moreover, it is also preferable that the coloring agent used in the coloring composition of the present invention is substantially only a pigment. When the colorant is substantially only a pigment, it means that the content of the pigment is 99% by mass or more, preferably 99.5% by mass or more, and particularly preferably only the pigment. . When the colorant used in the coloring composition of the present invention contains two or more pigments, at least one of the two or more pigments may be the above-described pigment A, but all pigments contained in the colorant is preferably Pigment A as described above.

The coloring agent used in the coloring composition of the present invention contains the above-described pigment A (a pigment having a long axis length/short axis length ratio of the short axis length to the long axis length of 1.4 or more). Is 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 80% by mass or more It is preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 95% by mass or more. The upper limit can be 100% by mass. It is also preferable that the coloring agent used in the coloring composition of the present invention is substantially only Pigment A. When the colorant is substantially only Pigment A, it means that the content of Pigment A is 99% by mass or more, preferably 99.5% by mass or more, and that the content is Pigment A only. is particularly preferred.

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

<<Resin>>
The coloring composition of the present invention contains a resin. The resin is blended, for example, for dispersing the pigment in the coloring composition or as a binder. A resin that is mainly used to disperse a pigment is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, and polyamideimide resins. , polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and the like. One of these resins may be used alone, or two or more may be mixed and used. In addition, resins described in paragraph numbers 0041 to 0060 of JP-A-2017-206689 and resins described in paragraph numbers 0022-0071 of JP-A-2018-010856 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 coloring composition can be improved, and pixels with excellent rectangularity can be easily formed. The acid group includes a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferred. A resin having an acid group can be used, for example, as an alkali-soluble resin.

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

The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferred to include repeating units derived from components.

式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の詳細については、特開２０１０－１６８５３９号公報の記載を参酌でき、この内容は本明細書に組み込まれる。In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), the description in JP-A-2010-168539 can be referred to, and the contents thereof are incorporated herein.

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

式（Ｘ）中、Ｒ_１は、水素原子またはメチル基を表し、Ｒ_２は炭素数２～１０のアルキレン基を表し、Ｒ_３は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。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).

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

For the resin having an acid group, JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408 The descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein. Moreover, resin which has an acid group can also use a commercial item.

The acid value of the resin having acid groups is preferably 30-500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, 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 acid group-containing resin is preferably 5,000 to 100,000. Moreover, the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.

Resins having an acid group include, for example, resins having the following structures.

The coloring composition of the present invention can also contain a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents 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 is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably from 40 to 105 mgKOH/g, more preferably from 50 to 105 mgKOH/g, even more preferably from 60 to 105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol % when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, it is possible to further suppress the generation of development residues when forming a pattern by photolithography.

It is also preferable that the resin used as the dispersant is a graft resin. Details of the graft resin can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

It is also preferable that the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. A resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.

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 portion. Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

Moreover, the above-described resin having an acid group (alkali-soluble resin) can also be used as a dispersant.

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in its side chain. The content of repeating units having an ethylenically unsaturated bond group in a side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70 mol, of the total repeating units of the resin. % is more preferred.

Dispersants are also available as commercial products, and specific examples thereof include BYK Chemie's DISPERBYK series (e.g., DISPERBYK-111, 161, etc.), Nippon Lubrizol Co., Ltd.'s Solsperse series ( For example, Solsperse 76500, etc.). Also, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can be used, the contents of which are incorporated herein. In addition, the resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.

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, 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 even more preferably 30% by mass or less. Also, the content of the resin having an acid group (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, 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 even more preferably 30% by mass or less. In addition, the content of the resin having an acid group (alkali-soluble resin) in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass, for the reason that excellent developability can be easily obtained. 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 applicability of the coloring composition. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph number 0223 of International Publication WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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 the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 ppm by mass or less, or 1 ppm by mass or less).

In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a mass ppt (parts per trillion) level organic solvent may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

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

The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.

In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.

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

In addition, it is preferable that the colored composition of the present invention does not substantially contain any environmentally regulated substances from the viewpoint of environmental regulations. In the present invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the colored composition is 50 ppm by mass or less, preferably 30 ppm by mass or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These comply with environmental regulations such as the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulation, the PRTR (Pollutant Release and Transfer Register) law, and the VOC (Volatile Organic Compounds) regulation. It is registered as a substance, and the amount used and handling methods are strictly regulated. These compounds may be used as a solvent when producing each component 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 safety to humans and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the amount of environmentally regulated substances, there is a method in which the system is heated or decompressed to raise the temperature to the boiling point of the environmentally regulated substances or higher, and the environmentally regulated substances are distilled off from the system. In the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like is added and distilled off under reduced pressure in order to suppress the radical polymerization reaction from progressing during the vacuum distillation and the intermolecular cross-linking. may These distillation methods include the stage of raw materials, the stage of products obtained by reacting raw materials (for example, resin solutions and polyfunctional monomer solutions after polymerization), or the stages of colored compositions prepared by mixing these compounds. is possible at any stage.

<<polymerizable compound>>
The coloring composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, known compounds that can be crosslinked by radicals, acids or heat can be used. In the present invention, the polymerizable compound is preferably, for example, a compound having an ethylenically unsaturated bond group. Examples of ethylenically unsaturated bond groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

The polymerizable compound may be in any chemical form such as monomer, prepolymer, oligomer, etc., but monomer is preferred. The molecular weight of the polymerizable compound is preferably 100-3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, even 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. Compounds containing 3 to 6 groups are more preferred. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of the polymerizable compound include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2008-292970. 2013-253224, paragraphs 0034 to 0038, JP 2012-208494, paragraph 0477, JP 2017-048367, JP 6057891, the compound described in JP 6031807 , the contents of which are incorporated herein.

As the polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. ), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues Compounds (eg SR454, SR499, commercially available from Sartomer) are preferred. Further, as the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toagosei), pentaerythritol 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 (manufactured by 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 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. can also

In addition, as the polymerizable compound, trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, isocyanuric acid ethyleneoxy-modified tri(meth)acrylate. , pentaerythritol tri(meth)acrylate and the like are also preferably used. 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 and 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 (manufactured by Nippon Kayaku Co., Ltd.) etc.

A compound having an acid group can also be used as the polymerizable compound. By using a polymerizable compound having an acid group, the polymerizable compound in an unexposed area is easily removed during development, and generation of development residue can be suppressed. The acid group includes a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferred. Commercially available polymerizable compounds having an acid group include Aronix M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The acid value of the polymerizable compound having an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the solubility in the developer is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling.

It is also a preferred embodiment that the polymerizable compound is a compound having a caprolactone structure. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

A polymerizable compound having an alkyleneoxy group can also be used as the polymerizable compound. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. A hexafunctional (meth)acrylate compound is more preferred. Commercially available polymerizable compounds having an alkyleneoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups and a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Sartomer Co., Ltd. KAYARAD TPA-330, which is an acrylate, and the like.

A polymerizable compound having a fluorene skeleton can also be used as the polymerizable compound. Commercially available polymerizable compounds having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

As the polymerizable compound, it is also preferable to use a compound that does not substantially contain environmental regulation substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the polymerizable compound include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. It is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-A-01-105238. Further, 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, UA-306I, AH-600 , T-600, AI-600, and LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

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 even more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less. The polymerizable compound may be used singly or in combination of two or more. When two or more are used in combination, it is preferable that the total of them falls within the above range.

Further, 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 from the viewpoint of curability, developability and film formation. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and even 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 to 300 parts by mass of the resin with respect to 100 parts by mass of the polymerizable compound. The lower limit is preferably 50 parts by mass or more, more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, more preferably 200 parts by mass or less.

<<Photoinitiator>>
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, compounds having photosensitivity to light in the ultraviolet range to the visible range are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazoles. dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, α-hydroxyketone compounds , α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Regarding the photopolymerization initiator, paragraphs 0065 to 0111 of JP-A-2014-130173 and Japanese Patent No. 6301489 can be referred to, the contents of which are incorporated herein.

Commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF). Commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication WO2015/ 152153, compounds described in WO2017/051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO2017/164127, etc. is mentioned. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), and Adeka Optomer N-1919. (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-14052). As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A-2014-137466. The contents of which are incorporated herein.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of. The contents of which are incorporated herein.

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

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication WO2015/036910.

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

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

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. Further, in the case of using a compound having an asymmetric structure, the crystallinity is lowered and the solubility in an organic solvent or the like is improved, making it difficult to precipitate over time, and it is possible to improve the stability over time of the colored composition. can. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include JP-A-2010-527339, JP-A-2011-524436, WO2015/004565, JP-A-2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication WO2017/033680, compound (E) and compound (E) described in JP 2013-522445 G), Cmpd1 to 7 described in International Publication WO2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP-A-2017-523465, JP-A-2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, and the like.

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, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, 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 kinds are used, it is preferable that the total amount thereof is within the above range.

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

式（Ｂ１）中、Ｐは色素構造を表し、Ｌは単結合または連結基を表し、Ｘは酸基、塩基性基、塩構造を有する基またはフタルイミドメチル基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なっていてもよい。

In formula (B1), P represents a dye 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 phthalimidomethyl group, and m is an integer of 1 or more. and n represents an integer of 1 or more, and when m is 2 or more, a plurality of Ls and Xs may be different from each other, and when n is 2 or more, a plurality of Xs may be different from each other.

The dye structure represented by P includes a pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, dianthraquinone dye structure, benzoisoindole dye structure, thiazineindigo dye structure, azo dye structure, and quinophthalone. dye structures, phthalocyanine dye structures, naphthalocyanine dye structures, dioxazine dye structures, perylene dye structures, perinone dye structures, benzimidazolone dye structures, benzothiazole dye structures, benzimidazole dye structures, benzoxazole dye structures, and the like.

The linking group represented by L includes a hydrocarbon group, a heterocyclic group, --NR--, --SO ₂ --, --S--, --O--, --CO-- or a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.

The acid group represented by X includes a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group, and the like. As the carboxylic acid amide group, a group represented by —NHCOR ^X1 is preferable. As the sulfonic acid amide group, a group represented by —NHSO ₂ R ^X2 is preferable. The imidic acid group is preferably a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ NHCOR ^X6 . R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon groups and heterocyclic groups represented by R ^X1 to R ^X6 may further have substituents. Further substituents are preferably halogen atoms, more preferably fluorine atoms. Basic groups represented by X include an amino group. The salt structure represented by X includes salts of the above-described acid group or basic group.

Pigment derivatives include compounds having the following structures. In addition, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03-153780 Publications, JP-A-03-045662, JP-A-04-285669, JP-A-06-145546, JP-A-06-212088, JP-A-06-240158, JP-A-10-30063, JP-A-10-195326, paragraph numbers 0086 to 0098 of international publication WO2011/024896, paragraph numbers 0063 to 0094 of international publication WO2012/102399, paragraph number 0082 of international publication WO2017/038252, etc. can also be used, the contents of which are incorporated herein.

The content of the pigment derivative is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, 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 even more preferably 15% by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination. When two or more are used in combination, the total amount thereof is preferably within the above range.

<<Compound Having a Cyclic Ether Group>>
The coloring composition of the present invention can contain a compound having a cyclic ether group. Cyclic ether groups include epoxy groups and oxetanyl groups. The compound having a cyclic ether group is preferably a compound having an epoxy group. Compounds having an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The upper limit of the number of epoxy groups can be, for example, 100 or less, 10 or less, or 5 or less. As the compound having an epoxy group, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408 The compounds described in JP-A-2017-179172 can also be used. The contents of these are incorporated herein.

The compound having an epoxy group may be a low-molecular compound (e.g., molecular weight less than 2000, further molecular weight less than 1000), or a macromolecule (e.g., molecular weight 1000 or more, in the case of a polymer, weight-average molecular weight 1000 or more). The weight average molecular weight of the epoxy group-containing compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

An epoxy resin can be preferably used as the compound having an epoxy group. Examples of epoxy resins include epoxy resins that are glycidyl etherified compounds of phenolic compounds, epoxy resins that are glycidyl etherified compounds of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester-based Epoxy resins, glycidylamine-based epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensation products of silicon compounds with epoxy groups and other silicon compounds, polymerizable unsaturated compounds with epoxy groups and other Examples include copolymers with other polymerizable unsaturated compounds. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g/eq, more preferably 310 to 1700 g/eq, even more preferably 310 to 1000 g/eq.

Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (these are epoxy group-containing polymers manufactured by NOF Corporation) and the like.

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, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, more preferably 10% by mass or less. Only one kind of compound having a cyclic ether group may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Silane coupling agent>>
The coloring composition of the present invention can contain a silane coupling agent. According to this aspect, the adhesion of the obtained membrane to the support can be improved. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred. Specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. the contents of which are incorporated herein.

The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.1 to 5 wt%. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The number of silane coupling agents may be one, or two or more. When two or more kinds are used, the total amount is preferably within the above range.

<<polymerization inhibitor>>
The coloring composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, 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.

<<Surfactant>>
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 surfactants can be used. For surfactants, reference can be made to paragraphs 0238 to 0245 of International Publication WO2015/166779, the contents of which are incorporated herein.

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

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the coloring composition.

As the fluorine-based surfactant, JP 2014-41318 Paragraph Nos. 0060 to 0064 (Corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- 132503, paragraphs 0117-0132, the contents of which are incorporated herein. Commercially available fluorosurfactants 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), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. .

Fluorine-based surfactants also include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), such as Megafac DS. -21.

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 fluorosurfactant. For such fluorine-based surfactants, the description in JP-A-2016-216602 can be referred to, the content of which is incorporated herein.

上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。A block polymer can also be used as the fluorosurfactant. Examples thereof include compounds described in JP-A-2011-89090. The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorosurfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.

A fluoropolymer having an ethylenically unsaturated bond group in a side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, such as Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorine-based surfactant.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) etc.

Examples of silicone-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, Toray Dow Corning Co., Ltd. ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie). A compound having the following structure can also be used as the silicon-based surfactant.

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Ultraviolet absorber>>
The coloring composition of the present invention can contain an ultraviolet absorber. A conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used as the ultraviolet absorber. For details of these, paragraph numbers 0052 to 0072 of JP-A-2012-208374, paragraph numbers 0317-0334 of JP-A-2013-068814, and paragraph numbers 0061-0080 of JP-A-2016-162946 are described. The contents of which can be referred to are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). Compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as ultraviolet absorbers.

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

<<Antioxidant>>
The coloring composition of the present invention can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. As antioxidants, 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, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Other Ingredients>>
The coloring composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. Moreover, the coloring composition of this invention may contain a latent antioxidant as needed. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication WO2014/021023, International Publication WO2017/030005, and JP-A-2017-008219. Commercially available products include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).

Moreover, the coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. 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 1-100 nm, more preferably 3-70 nm, and most preferably 5-50 nm. The metal oxide may have a core-shell structure, in which case the core may be hollow.

In addition, the coloring composition of the present invention may contain a light fastness improver. As the light resistance improver, compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of International Publication WO2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds described in paragraph numbers 0018-0021 of JP-A-2012-103475, in particular Compounds described in paragraphs 0015 to 0018 of JP 2011-257591, compounds described in paragraphs 0017 to 0021 of JP 2011-191483, described in paragraphs 0108 to 0116 of JP 2011-145668 and compounds described in paragraph numbers 0103 to 0153 of JP-A-2011-253174.

In the coloring composition of the present invention, the content of free metals that are not bound or coordinated with pigments is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less. , is particularly preferably substantially free. According to this aspect, stabilization of pigment dispersibility (prevention of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuations due to elution of metal atoms and metal ions, Display characteristics can be improved. In addition, JP-A-2012-153796, JP-A-2000-345085, JP-A-2005-200560, JP-A-08-043620, JP-A-2004-145078, JP-A-2014-119487, Described in JP 2010-083997, JP 2017-090930, JP 2018-025612, JP 2018-025797, JP 2017-155228, JP 2018-036521, etc. You can also get the effect of Examples of the free metal types include 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 and the like are included. Further, in the coloring composition of the present invention, the content of free halogen that is not bonded or coordinated with the pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, and 10 ppm or less. It is more preferable, and it is particularly preferable that it does not contain substantially. Halogens include F, Cl, Br, I and their anions. Methods for reducing free metals and halogens in the colored composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

It is also preferred that the coloring composition of the present invention does not contain a terephthalate ester.

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

<Container>
The container for the coloring composition of the present invention is not particularly limited, and known containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins for the purpose of suppressing contamination of raw materials and coloring compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.

<Method for producing colored composition>
The coloring composition of the present invention can be produced by mixing the aforementioned components. In the production of the colored composition, all components may be dissolved and / or dispersed in an organic solvent at the same time to produce a colored composition, or if necessary, each component may be appropriately mixed into two or more solutions or dispersions. As, at the time of use (at the time of coating) these may be mixed to produce a colored composition.

Moreover, it is preferable that a process of dispersing the pigment is included in the production of the coloring composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing pigments are described in ``Dispersion Technology Encyclopedia, Information Organization Co., Ltd., July 15, 2005'' and ``Dispersion Technology Centered on Suspension (Solid/Liquid Dispersion System) and Industrial Applications'' The process and disperser described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the pigment, the particles may be made finer in the salt milling process. Materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.

In producing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene, polypropylene (PP) (high density, ultra high molecular weight (including polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like can be used as filters.

It is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.

<Membrane>
The film of the present invention is a film obtained from the colored composition of the present invention described above. The film of the present invention can be used for color filters and the like. Specifically, it can be preferably used as a colored layer (pixel) of a color filter, and more preferably used as a red colored layer (red pixel) of a color filter. The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, 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.

<Color filter>
Next, the color filter of the present invention will be explained. The color filter of the invention has the film of the invention described above. More preferably, it has the film of the present invention as a pixel of a color filter. The color filter of the present invention can be used for solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), image display devices, and the like.

In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, 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 still more preferably 0.3 μm or more.

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

Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco. Also, the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.). Moreover, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω·cm or more, more preferably 10 ¹¹ Ω·cm or more. Although the upper limit is not specified, it is preferably 10 ¹⁴ Ω·cm or less, for example. The volume resistance value of the pixel can be measured using, for example, a super-high resistance meter 5410 (manufactured by Advantest).

Also, 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 the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01-10 μm, more preferably 0.1-5 μm. Examples of the method of forming the protective layer include a method of applying a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides. Resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, urethane resins, aramid resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluorine Resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ and the like, and two or more of these components may be contained. _For example, in the case of a protective layer intended to block oxygen, the protective layer preferably contains a polyol resin, _SiO2 , _Si2N4 . In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin or a fluororesin.

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

The protective layer contains additives such as organic/inorganic fine particles, absorbers for specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, surfactants, etc., as necessary. You can Examples of organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. A known absorber can be used as the absorber for the specific wavelength. Examples of the ultraviolet absorbent and the near-infrared absorbent include the materials described above. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total weight of the protective layer.

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

The color filter may have a structure in which pixels (colored layers) of each color are embedded in regions partitioned by partition walls. The partition in this case preferably has a low refractive index for each pixel. Moreover, the partition may be formed with the configuration described in US2018/0040656.

<Manufacturing method of color filter>
Next, a method for manufacturing the color filter of the present invention will be described. The color filter of the present invention comprises a step of forming a colored composition layer on a support using the above-described colored composition of the present invention, a step of forming a pattern on the colored composition layer by photolithography, can be manufactured through Pattern formation by photolithography preferably includes a step of patternwise exposing the colored composition layer and a step of developing and removing unexposed portions of the colored composition layer to form a pattern (pixels). If necessary, a step of baking the coloring composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided. Each step will be described below.

In the step of forming the colored composition layer, the colored composition of the present invention is used to form the colored composition layer on the support. The support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. In some cases, the silicon substrate is formed with a black matrix that isolates each pixel. In addition, the silicon substrate may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate.

A known method can be used as a method for applying the coloring composition. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the method of applying the coloring composition, the descriptions in International Publication WO2017/030174 and International Publication WO2017/018419 can be referred to, and the contents thereof are incorporated herein.

The coloring composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process. 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, for example, 50° C. or higher, and can also be 80° C. or higher. The pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

Next, the colored composition layer is patternwise exposed (exposure step). For example, the colored composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable. A long-wave light source of 300 nm or more can also be used.

Further, the exposure may be performed by continuously irradiating the light, or by pulsing the light (pulse exposure). Note that the pulse exposure is an exposure method in which light irradiation and pause are repeated in a cycle of short time (for example, less than millisecond level). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more. The frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, and even more preferably 4 kHz or higher. 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 50000000 W/ ^m2 or more, more preferably 100000000 W/ ^m2 or more, and even more preferably 200000000 W/ ^m2 or more. 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 even more preferably 500000000 W/m ² or less. It should be noted that the pulse width is the time during which the light is applied in the pulse period. Also, the frequency is the number of pulse cycles per second. Further, the maximum instantaneous illuminance is the average illuminance within the time during which the light is irradiated in the pulse period. Further, the pulse cycle is a cycle in which light irradiation and rest in pulse exposure are set as one cycle.

The dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be selected as appropriate, and in addition to exposure in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free) or in a high-oxygen atmosphere 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 set as appropriate, and is usually selected from the range of 1000 W/m ² to 100000 W/m ² (eg, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). can be done. The oxygen concentration and exposure illuminance may be appropriately combined. For example, the illuminance may be 10000 W/m ² at an oxygen concentration of 10% by volume and 20000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed portion of the colored composition layer is removed by development to form a pattern (pixels). The development and removal of the unexposed portion of the colored composition layer can be performed using a developer. As a result, the unexposed portion of the colored composition layer in the exposure step is eluted into the developer, leaving only the photocured portion. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

Examples of the developer include organic solvents and alkaline developers. The alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene. Alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. Examples of surfactants include the surfactants described above, and nonionic surfactants are preferred. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinsing solution to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.

It is also preferable to carry out additional exposure treatment and heat treatment (post-baking) after drying after development. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Further, the additional exposure processing may be performed by the method described in KR1020170122130A.

<Solid-state image sensor>
The solid-state imaging device of the present invention has the film of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device.

A plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication WO2018/043654. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.

<Image display device>
The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. For a definition of an image display device and details of each image display device, see, for example, "Electronic Display Device (written by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (written by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

<Measurement of weight average molecular weight (Mw) of resin)
The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) under the following conditions.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 connected Column developing solvent: Tetrahydrofuran Column temperature: 40°C
Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1% by mass)
Device name: Tosoh HLC-8220GPC
Detector: RI (refractive index) detector calibration curve Base resin: polystyrene resin

<Measurement of short axis length and long axis length of pigment>
Using a scanning electron microscope, an image taken at an acceleration voltage of 5 kV and an imaging magnification of 100,000 times is digitized, and image luminance data in the long axis direction and short axis direction of the pigment (coordinates in the long axis direction, coordinates in the short axis direction) , and luminance). In the digitization, the image was divided into 1280 in the width direction, processed with 8-bit luminance to obtain data of 256 gradations, and the image luminance of each divided coordinate point was converted into a predetermined gradation value. Next, in the obtained image brightness data, the coordinate in the direction corresponding to the long axis of the particle is taken as the horizontal axis, and the average value of brightness at each coordinate point in the long axis direction (that is, the average value of brightness at each coordinate point divided by 1280) ) on the vertical axis to create a luminance curve. A differential curve was created by differentiating the created brightness curve, and the coordinates of the boundary of the pigment were specified from the peak position of the created differential curve. The operation of taking the coordinate in the direction corresponding to the major axis of the pigment as the horizontal axis was repeated three times, and the longest axis length was taken as the major axis length. The operation of setting the coordinates on the horizontal axis was repeated three times in the short axis direction, and the shortest axis length was taken as the short axis length. Specifically, the length of the major axis is defined as the axis (straight line) that allows the longest particle length to be determined as the major axis. On the other hand, the minor axis was determined as the axis having the longest length when the particle length was taken by a straight line orthogonal to the major axis, and the length of this axis was taken as the minor axis length.
In addition, the arithmetic average value of the minor axis length and the major axis length of 100 pigments was calculated to calculate the average minor axis length of the pigment and the average major axis length of the pigment.

分散剤Ｄ１：下記構造の樹脂（Ｍｗ＝２４０００、主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。）

<Preparation of pigment dispersion>
(Pigment Dispersions A1-1 to A1-7)
C. I. 9 parts by weight of Pigment Green 58, C.I. I. Pigment Yellow 185 6 parts by mass, 2.5 parts by mass of pigment derivative Y1, 5 parts by mass of dispersing agent D1, and 77.5 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were added to a mixed liquid having a diameter of After adding 230 parts by mass of zirconia beads of 0.3 mm and performing dispersion treatment using a paint shaker, the beads were separated by filtration to prepare pigment dispersions 1-1 to A1-7. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. By changing the dispersion time, the major axis length and the minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the table below. These pigment dispersions had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.
Pigment derivative Y1: a compound having the following structure.

Dispersant D1: Resin having the following structure (Mw = 24000, the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.)

(Pigment Dispersions A2-1 to A2-7)
C. I. 9 parts by weight of Pigment Green 36, C.I. I. Pigment Yellow 150 of 6 parts by mass, pigment derivative Y1 of 2.5 parts by mass, dispersant D1 of 5 parts by mass, and PGMEA of 77.5 parts by mass were mixed, and zirconia beads 230 having a diameter of 0.3 mm were added. After adding parts by mass and performing dispersion treatment using a paint shaker, the beads were separated by filtration to prepare pigment dispersions A2-1 to A2-7. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. By changing the dispersion time, the major axis length and the minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the table below. These pigment dispersions had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.

(Pigment dispersion liquid A3)
C. I. 9 parts by weight of Pigment Green 58, C.I. I. Pigment Yellow 139 of 6 parts by mass, pigment derivative Y1 of 2.5 parts by mass, dispersant D1 of 5 parts by mass, and PGMEA of 77.5 parts by mass were added to a mixed liquid, and zirconia beads 230 having a diameter of 0.3 mm were added. After adding parts by mass and performing a dispersion treatment using a paint shaker, the beads were separated by filtration to prepare a pigment dispersion liquid A3. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. This pigment dispersion had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.

(Pigment dispersion liquid A4)
C. I. Pigment Red 254, 10.5 parts by mass, C.I. I. Pigment Yellow 139 of 4.5 parts by mass, pigment derivative Y1 of 2.0 parts by mass, dispersant D1 of 5.5 parts by mass, and PGMEA of 77.5 parts by mass were added to a mixed liquid having a diameter of 0.3 mm. 230 parts by mass of zirconia beads were added, and dispersion treatment was performed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersion liquid A4. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. This pigment dispersion had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.

分散剤Ｄ２：下記構造の化合物

(Pigment dispersion A5-1, A5-2)
C. I. Pigment Red 177, 10.5 parts by mass, C.I. I. Pigment Yellow 139 4.5 parts by mass, 2.0 parts by mass of pigment derivative Y2, 5.5 parts by mass of dispersant D2, and 77.5 parts by mass of PGMEA 230 parts by mass of zirconia beads were added and dispersed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersions A5-1 and A5-2. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. By changing the dispersion time, the major axis length and the minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the table below. These pigment dispersions had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.
Pigment derivative Y2: a compound having the following structure

Dispersant D2: a compound having the following structure

(Pigment dispersion liquid A6)
C. I. Pigment Red 264, 10.5 parts by mass, C.I. I. Pigment Yellow 139 of 4.5 parts by mass, pigment derivative Y1 of 2.0 parts by mass, dispersant D1 of 5.5 parts by mass, and PGMEA of 77.5 parts by mass were added to a mixed liquid having a diameter of 0.3 mm. 230 parts by mass of zirconia beads were added, and dispersion treatment was performed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersion liquid A6. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. This pigment dispersion had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.

(Pigment dispersion liquid A7)
C. I. Pigment Red 272, 10.5 parts by mass, C.I. I. Pigment Yellow 139 of 4.5 parts by mass, pigment derivative Y1 of 2.0 parts by mass, dispersant D1 of 5.5 parts by mass, and PGMEA of 77.5 parts by mass were added to a mixed liquid having a diameter of 0.3 mm. 230 parts by mass of zirconia beads were added, and dispersion treatment was performed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersion liquid A7. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. This pigment dispersion had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.

(Pigment dispersion liquid A8)
10.5 parts by mass of red pigment 1, C.I. I. Pigment Yellow 139 of 4.5 parts by mass, pigment derivative Y1 of 2.0 parts by mass, dispersant D1 of 5.5 parts by mass, and PGMEA of 77.5 parts by mass were added to a mixed liquid having a diameter of 0.3 mm. 230 parts by mass of zirconia beads were added, and dispersion treatment was performed using a paint shaker, and then the beads were separated by filtration to prepare pigment dispersion liquid A8. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. This pigment dispersion had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.
Red pigment 1: a compound having the following structure

(Pigment dispersion A9-1, A9-2)
C. I. Pigment Blue 15:6, 12 parts by weight of C.I. I. Pigment Violet 23 of 3 parts by mass, pigment derivative Y1 of 2.7 parts by mass, dispersant D1 of 4.8 parts by mass, and PGMEA of 77.5 parts by mass were added to a mixed liquid containing zirconia having a diameter of 0.3 mm. After adding 230 parts by mass of beads and performing dispersion treatment using a paint shaker, the beads were separated by filtration to prepare pigment dispersions A9-1 and A9-2. The long axis length and short axis length of Pigment 1 and Pigment 2 contained in the pigment dispersion liquid were the values shown in the table below. By changing the dispersion time, the major axis length and the minor axis length of Pigment 1 and Pigment 2 were adjusted to the values shown in the table below. These pigment dispersions had a solid concentration of 22.5% by mass and a pigment content of 15% by mass.

(Pigment dispersion liquid A10)
C. I. 12 parts by weight of Pigment Blue 15:6, 3 parts by weight of V dye 1 described in paragraph number 0292 of JP-A-2015-041058, 2.7 parts by weight of pigment derivative Y1, 4.8 parts by weight 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 to the mixture, and after dispersion treatment was performed using a paint shaker, the beads were separated by filtration. to prepare a pigment dispersion A10. The major axis length and minor axis length of Pigment 1 contained in the pigment dispersion were the values shown in the table below. This pigment dispersion had a solid concentration of 22.5% by mass and a colorant content (total amount of pigment and dye) of 15% by mass.

The abbreviations in the above table are as follows.
PG36: C.I. I. pigment green 36
PG58: C.I. I. pigment green 58
PR254: C.I. I. pigment red 254
PR264: C.I. I. pigment red 264
PR272: C.I. I. pigment red 272
Red pigment 1: compound having the structure described above PR177: C.I. I. pigment red 177
PB15:6: C.I. I. pigment blue 15:6
PY185: C.I. I. pigment yellow 185
PY150: C.I. I. pigment yellow 150
PY139: C.I. I. pigment yellow 139
PV23: C.I. I. pigment violet 23

<Preparation of coloring composition>
After mixing the raw materials shown in the table below, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a colored composition. Compositions 101 to 118 and C101 to C103 were green colored compositions, compositions 201 to 205 and C201 were red colored compositions, and compositions 301, 302 and C301 were blue colored compositions.

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

(Pigment dispersion)
Pigment dispersions A1-1 to A1-7, A2-1 to A2-7, A3, A4, A5-1, A5-2, A6, A7, A8, A9-1, A9-2, A10: pigments as described above Dispersions A1-1 to A1-7, A2-1 to A2-7, A3, A4, A5-1, A5-2, A6, A7, A8, A9-1, A9-2, A10

(resin)
B1: Resin having the following structure (numerical values attached to the main chain are molar ratios: Mw: 10,000, acid value: 70 mgKOH/g, C=C value: 1.4 mmol/g)

(Polymerizable monomer)
M1: Ogsol EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton, C=C value: 2.1 mmol/g)
M2: compound having the following structure (C=C value: 10.4 mmol/g)

(initiator)
I1, I3, I5: compounds having the following structures

(Surfactant)
W1: a compound having the following structure

(Additive)
T1: EHPE3150 (manufactured by Daicel Corporation, epoxy resin)
T2: compound having the following structure (silane coupling agent)

<Evaluation of membrane shrinkage>
CT-4000 (manufactured by Fuji Film Electronic Materials Co., Ltd.) was applied on a glass substrate by spin coating so that the film thickness was 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. A stratum was formed. On the glass substrate with the underlayer, each coloring composition is applied by spin coating so that the film thickness after post-baking becomes the film thickness shown in the table below, and then at 100 ° C. using a hot plate. Heated for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), i-line was irradiated onto the entire surface of the glass substrate through an open frame mask at an exposure dose of 1000 mJ/cm ² for exposure. Then, a film was formed by heating at 200° C. for 5 minutes using a hot plate. The film thickness of the obtained film was measured using a palpable profiling system DektakXT (manufactured by BRUKER).
Next, the film prepared above was allowed to stand for 100 hours under constant temperature and humidity at a temperature of 110° C. and a humidity of 85%. After the moisture resistance test, the thickness of the film was measured, the shrinkage rate of the film was measured from the following formula, and the film shrinkage was evaluated according to the following criteria. The thickness of the film was measured before and after the moisture resistance test at five equally divided positions on the glass substrate in the diameter direction, and the average value was adopted.
Film shrinkage rate (%) = {(film thickness before moisture resistance test - film thickness after humidity resistance test) / film thickness before humidity resistance test} × 100
(Evaluation criteria)
A: Shrinkage rate of film is less than 5% B: Shrinkage rate of film is 5% or more and less than 10% C: Shrinkage rate of film is 10% or more and less than 20% D: Shrinkage rate of film is 20 % or more

<Evaluation of color value>
A coloring composition shown in the table below was applied onto a glass substrate by spin coating. Then, using a hot plate, the film was heated at 100° C. for 2 minutes to form a film having the film thickness shown in the table below. Light of the wavelengths shown in the table below is incident on the obtained film, and the transmittance is measured with a spectrometer (UV4100, manufactured by Hitachi High-Technologies Corporation) to measure the optical density (OD value). bottom.
By normalizing the obtained optical density with the film thickness, the relative value of the color value was obtained. In addition, light with a wavelength of 660 nm was incident on the film formed using the green colored composition. In addition, light with a wavelength of 530 nm was incident on the film that was formed using the red colored composition. In addition, light with a wavelength of 610 nm was incident on the film formed using the blue colored composition.

<Evaluation of pattern formability and residue>
An 8-inch (20.32 cm) silicon wafer is coated with CT-4000L (manufactured by Fuji Film Electronic Materials Co., Ltd.) using a spin coater so that the thickness becomes 0.1 μm after post-baking, and a hot plate is applied. and heated at 220° C. for 300 seconds to form an undercoat layer to obtain a silicon wafer with an undercoat layer.
Then, each coloring composition was applied by a spin coating method so that the film thickness after post-baking would be the film thickness shown in the table below. Then, using a hot plate, it was post-baked at 100° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), an exposure amount of 200 mJ/cm ² is applied through a mask having a Bayer pattern formed with a pixel (pattern) size of 1 μm square. Line exposed. Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, using a hot plate, heating was performed at 200° C. for 5 minutes to form pixels (patterns).

(Evaluation method for pattern formability)
The image portion (pattern) of the obtained pixels was observed using a high-resolution FEB (Field Emission Beam) measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Technologies Corporation).
A: The pattern with the target line width was formed without distortion, and the difference between the line width at the center of the pattern and the line width at the edge was less than 5%.
B: A pattern with approximately the target line width was formed, but the difference between the line width at the center of the pattern and the line width at the edge was 5% or more and less than 10%.
C: A pattern with almost the target line width was formed, but the difference between the line width at the center of the pattern and the line width at the edge was 10% or more and less than 30%.
D: Other than A to C, or no pattern could be formed.

(Residue evaluation method)
The resulting pixels were observed for residues in non-image areas (between pixels) using a high-resolution FEB (Field Emission Beam) measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Technologies Corporation).
A: No residue is observed.
B: Residue was observed in a region of more than 0% and less than 5% of the non-image area.
C: Residue was observed in a region of 5% or more and less than 10% of the non-image area.
D: Residue was found in 10% or more of the non-image area.

As shown in the table above, all of Examples using Compositions 101 to 118, 201 to 205, 301 and 302 were able to form films with suppressed film shrinkage. Furthermore, the evaluation of pattern formability and residue was also good. Further, as is clear from the results of Examples 101 and 107 to 111 and the results of Test Examples 112 to 117, the long axis length/short axis length value is 1.4 or more and 3.0 or less. , a film with a higher color value could be formed.

(Test Example 1001)
A green composition was applied onto a silicon wafer by spin coating so that the film thickness after post-baking was 1.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm was exposed through a 2 μm square dot pattern mask with an exposure amount of 1000 mJ/cm ² . Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, the green composition was patterned by heating (post-baking) at 200° C. for 5 minutes using a hot plate. Similarly, the Red composition and the Blue composition were sequentially patterned to form red, green and blue colored patterns (Bayer patterns).
Composition 101 was used as the Green composition. Composition 201 was used as the Red composition. Composition 301 was used as the Blue composition.
Note that the Bayer pattern is one red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. ) elements.
The obtained color filter was incorporated into a solid-state imaging device according to a known method. This solid-state imaging device had a favorable image recognition ability.

Claims (22)

A coloring composition comprising a coloring agent, a resin, a photopolymerization initiator, a polymerizable compound and an organic solvent,
Containing 50% by mass or more of the coloring agent in the total solid content of the coloring composition,
The colorant is at least one selected from green pigments, red pigments, blue pigments, yellow pigments, and violet pigments, and the value of long axis length/short axis length, which is the ratio of short axis length to long axis length, is Containing 40% by mass or more of pigment A of 2.0 or more,
The polymerizable compound is a compound having an ethylenically unsaturated bond group,
The total content of the polymerizable compound and the resin in the total solid content of the coloring composition is 10 to 65 mass%, relative to 100 parts by mass of the polymerizable compound, containing 30 to 300 parts by mass of the resin , coloring composition. A coloring composition containing a coloring agent, a resin, a polymerizable compound and an organic solvent,
Containing 50% by mass or more of the coloring agent in the total solid content of the coloring composition,
The colorant contains 40% by mass or more of a pigment A having a value of 1.4 or more of the long axis length/short axis length, which is the ratio of the short axis length to the long axis length,
The coloring composition, wherein the polymerizable compound comprises a polymerizable compound having a fluorene skeleton and a compound containing 3 or more ethylenically unsaturated bond groups. A coloring composition comprising a coloring agent, a resin, a photopolymerization initiator, a polymerizable compound and an organic solvent,
Containing 50% by mass or more of the coloring agent in the total solid content of the coloring composition,
The colorant is at least one selected from Color Index Pigment Red 264, Color Index Pigment Red 272, and Color Index Pigment Green 58, and the ratio of major axis length to minor axis length is Containing 40% by mass or more of pigment A having a length value of 1.4 or more,
The polymerizable compound is a compound having an ethylenically unsaturated bond group,
The total content of the polymerizable compound and the resin in the total solid content of the coloring composition is 10 to 65 mass%, relative to 100 parts by mass of the polymerizable compound, containing 30 to 300 parts by mass of the resin , coloring composition. 4. The coloring composition of claim 3, wherein Pigment A is Color Index Pigment Green 58. The coloring composition according to any one of claims 1 to 4, which is a coloring composition for forming pixels of a color filter. The coloring composition according to any one of claims 1 to 5, which contains 60% by mass or more of the coloring agent in the total solid content of the coloring composition. The coloring composition according to claim 2 or 3, wherein the pigment A has a long axis length/short axis length value of 1.4 or more and 3.0 or less. The coloring composition according to any one of claims 1 to 7, wherein the pigment A has an average long axis length of 15 to 150 nm. The coloring composition according to any one of claims 1 to 7, wherein the pigment A has an average minor axis length of 10 to 100 nm. 3. The coloring composition according to claim 1, wherein the pigment A is a red pigment. 11. The coloring composition according to claim 10, wherein the red pigment is at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 264, and Color Index Pigment Red 272. 3. The colored composition according to claim 2 , comprising a photoinitiator and a polymerizable compound. The coloring composition according to any one of claims 1 to 12, wherein the resin comprises an alkali-soluble resin. The coloring composition according to any one of claims 1 to 13, which is used for pattern formation by photolithography. The coloring composition according to any one of claims 1 to 14, which is for a solid-state imaging device. The coloring composition according to any one of claims 1 to 14, which is for color filters. 17. The coloring composition according to claim 16, which is for red pixel formation. A film obtained from the colored composition according to any one of claims 1-17. A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 17, and a step of forming a pattern on the colored composition layer by photolithography. A method for manufacturing a color filter having A color filter comprising the film according to claim 18. A solid-state imaging device comprising the film according to claim 18 . An image display device comprising the film according to claim 18 .