JP7057412B2 - Coloring composition, pigment dispersion, method for producing pigment dispersion, cured film, color filter, solid-state image sensor and image display device - Google Patents

Description

The present invention relates to a coloring composition, a pigment dispersion, a method for producing a pigment dispersion, a cured film, a color filter, a solid-state image sensor, and an image display device.

In recent years, with the widespread use of digital cameras, camera-equipped mobile phones, and the like, demand for solid-state image sensors such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as key devices for displays and optical elements.

In color filters, attempts have been made to adjust the spectroscopy by using a plurality of pigments in combination. For example, Patent Documents 1 to 5 describe forming green pixels in a color filter by using a coloring composition containing a green pigment and a yellow pigment.

Japanese Patent Application Laid-Open No. 2003-185830 Japanese Unexamined Patent Publication No. 2015-102612 JP-A-2015-09613 Japanese Unexamined Patent Publication No. 2015-052779 Japanese Unexamined Patent Publication No. 2014-041341

It is desired that the color filter has high color separation and high rectangularity. In recent years, these characteristics have been sought at a higher level.

Therefore, an object of the present invention is to provide a coloring composition which is excellent in color separation and can form a pattern having high rectangularity. Another object of the present invention is to provide a pigment dispersion, a method for producing a pigment dispersion, a cured film, a color filter, a solid-state image sensor, and an image display device.

According to the study of the present inventor, it has been found that the above object can be achieved by using a specific green pigment and a yellow pigment, and the present invention has been completed. The present invention provides:
<1> Contains a green pigment, a yellow pigment, a photopolymerization initiator, a polymerizable compound and a solvent.
The green pigment comprises at least Color Index Pigment Green 36 and Color Index Pigment Green 7.
The yellow pigment comprises at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.
A coloring composition in which the mass ratio of the color index pigment green 36 to the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50.
<2> The coloring composition according to <1>, wherein the mass ratio of the color index pigment green 36 and the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 30: 70 to 45:55. ..
<3> The coloring composition according to <1> or <2>, which contains 50 to 100 parts by mass of a yellow pigment with respect to 100 parts by mass of a green pigment.
<4> The mass ratio of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 is Color Index Pigment Yellow 139: Color Index Pigment Yellow 150 = 0.1: 99.9 to 20:80, <1> to The coloring composition according to any one of <3>.
<5> For a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7, Color Index Pigment Yellow 139 is 0.05 to 20 parts by mass, and Color Index Pigment Yellow 150 is 49.95 to The coloring composition according to any one of <1> to <4>, which contains 99.9 parts by mass.
<6> A total of 50 to 100 parts by mass of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 is included in a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7, <1> to The coloring composition according to any one of <5>.
<7> For 100 parts by mass of Color Index Pigment Green 36, 0.1 to 80 parts by mass of Color Index Pigment Yellow 139 and 99.9 to 399.6 parts by mass of Color Index Pigment Yellow 150 are included. 1> The coloring composition according to any one of <6>.
<8> The coloring composition according to any one of <1> to <7>, wherein the polymerizable compound contains a polymerizable compound having an alkyleneoxy group.
<9> The coloring composition according to any one of <1> to <8>, further comprising a resin.
<10> The coloring composition according to <9>, wherein the resin contains a resin containing a repeating unit having a nitrogen atom in the main chain.
<11> The coloring composition according to <9>, wherein the resin contains an alkali-soluble resin having a polymerizable group.
<12> The coloring composition according to any one of <1> to <11>, further comprising an ultraviolet absorber.
<13> The coloring composition according to any one of <1> to <12>, which is a coloring composition for forming green pixels in a color filter.
<14> Contains green pigment, yellow pigment and solvent, the green pigment contains at least color index pigment green 36 and color index pigment green 7, and the yellow pigment contains at least color index pigment yellow 139 and color index pigment yellow 150. , The pigment dispersion having a mass ratio of color index pigment green 36 and color index pigment green 7 of color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50.
<15> The method for producing a pigment dispersion liquid according to <14>.
A method for producing a pigment dispersion, which comprises a step of co-dispersing Color Index Pigment Green 36, Color Index Pigment Green 7, Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 in the presence of a solvent.
<16> A cured film obtained from the coloring composition according to any one of <1> to <13>.
<17> A color filter containing the cured film according to <16>.
<18> A solid-state image sensor having the color filter according to <17>.
<19> An image display device having the color filter according to <17>.

According to the present invention, it is possible to provide a coloring composition having excellent color separation and capable of forming a pattern having high rectangularity. Further, it is possible to provide a pigment dispersion liquid, a method for producing a pigment dispersion liquid, a cured film, a color filter, a solid-state image pickup device, and an image display device.

Hereinafter, the contents of the present invention will be described in detail.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "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).
In the present specification, "exposure" means not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Further, examples of the light used for exposure generally include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present specification, the total solid content means the total amount of the components excluding the solvent from all the components of the composition.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Allyl ”represents both allyl and / or methacrylic, and“ (meth) acryloyl ”represents both / or either acryloyl and methacrylic acid.
As used herein, the term "process" not only means an independent process, but also the term "process" as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. include.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values measured by gel permeation chromatography (GPC).

<Coloring composition>
The coloring composition of the present invention contains a green pigment, a yellow pigment, a photopolymerization initiator, a polymerizable compound and a solvent.
The green pigment comprises at least Color Index Pigment Green 36 and Color Index Pigment Green 7.
The yellow pigment comprises at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.
The mass ratio of the color index pigment green 36 to the color index pigment green 7 is characterized in that the color index pigment green 36: the color index pigment green 7 = 25: 75 to 50:50.

The coloring composition of the present invention contains the above-mentioned predetermined green pigment and yellow pigment, and the mass ratio of the color index pigment green 36 and the color index pigment green 7 is within the above-mentioned range, so that the color is red or blue. It is possible to form a cured film suitable for green pixels having spectral characteristics excellent in color separation from the above. In particular, it is possible to form a cured film having a high transmittance of light in the wavelength range of 500 to 550 nm and a high shielding property against light in the wavelength range of 400 to 470 nm and light in the wavelength range of 600 to 700 nm. Furthermore, the coloring composition of the present invention can form a highly rectangular pattern. The reason why a highly rectangular pattern can be formed by the coloring composition of the present invention is that the above-mentioned predetermined green pigment and the yellow pigment are used in combination and the mass ratio of the predetermined green pigment is within the above-mentioned range. It is presumed that this is because the transparency of the light used for exposure such as i-line in the composition is appropriately adjusted.

In the coloring composition of the present invention, the ratio (A _min / A ₄₅₀ ) of the minimum value A _min of the absorbance to light having a wavelength of 500 to 550 nm and the absorbance A ₄₅₀ to light having a wavelength of 450 nm is 0.02 to 0.09. It is preferably 0.03 to 0.08, more preferably 0.04 to 0.07, and even more preferably 0.04 to 0.07. Further, the ratio (A _min / A ₆₀₀ ) of the minimum value A _min of the absorbance for light having a wavelength of 500 to 550 nm and the absorbance A ₆₀₀ for light having a wavelength of 600 nm is preferably 0.04 to 0.17, and is 0. It is more preferably .06 to 0.15, and even more preferably 0.08 to 0.13.
The coloring composition of the present invention transmits light in the wavelength range of 400 to 700 nm in the thickness direction of the film when a film having a film thickness of 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm after drying is formed. In the spectrum, the wavelength λ1 on the longer wave side than the wavelength of the peak value having the peak value of the transmittance in the wavelength range of 500 to 550 nm and the transmittance being 50% of the peak value and the shorter wave than the wavelength of the peak value. The difference (λ1-λ2) from the wavelength λ2 on the side is preferably 90 to 112 nm, more preferably 93 to 109 nm, and even more preferably 95 to 107 nm.
Further, the coloring composition of the present invention is used for light having a wavelength of 400 to 700 nm in the thickness direction of the film when a film having a film thickness of 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm after drying is formed. The maximum value of the transmittance is preferably 80% or more, more preferably 83% or more, and further preferably 85% or more. Further, the average transmittance for light having a wavelength of 475 to 585 nm is preferably 60% or more, more preferably 65% or more, still more preferably 67% or more. Further, the transmittance for light having a wavelength of 450 nm is preferably 20% or less, more preferably 15% or less, still more preferably 13% or less. Further, the transmittance for light having a wavelength of 600 nm is preferably 40% or less, more preferably 35% or less, and further preferably 33% or less.

The coloring composition of the present invention can be preferably used for forming green pixels in a color filter. Hereinafter, each component used in the coloring composition of the present invention will be described.

<< Green Pigment and Yellow Pigment >>
The coloring composition of the present invention comprises a green pigment containing at least Color Index Pigment Green 36 and Color Index Pigment Green 7, and a yellow pigment containing at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.

In the coloring composition of the present invention, the mass ratio of the color index pigment green 36 and the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50, and 30: 70 to. It is preferably 45:55, more preferably 35:65 to 40:60. When the mass ratio of the two is in the above range, it is possible to form a cured film suitable for green pixels having spectral characteristics excellent in color separation from red and blue.

In the coloring composition of the present invention, the mass ratio of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 is Color Index Pigment Yellow 139: Color Index Pigment Yellow 150 = 0.1: 99.9 to 20:80. It is preferably 1:99 to 15:85, more preferably 3:97 to 10:90, and even more preferably 3:97 to 10:90.

The coloring composition of the present invention preferably contains 0.05 to 20 parts by mass of Color Index Pigment Yellow 139 with respect to a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. The lower limit is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2.0 parts by mass or more.

The coloring composition of the present invention preferably contains 0.1 to 80 parts by mass of Color Index Pigment Yellow 139 with respect to 100 parts by mass of Color Index Pigment Green 36. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less. The lower limit is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more.

The coloring composition of the present invention preferably contains 49.95 to 99.9 parts by mass of Color Index Pigment Yellow 150 with respect to a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7. The upper limit is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and further preferably 85 parts by mass or less. The lower limit is preferably 50 parts by mass or more, and more preferably 51 parts by mass or more.

The coloring composition of the present invention preferably contains 99.9 to 399.6 parts by mass of Color Index Pigment Yellow 150 with respect to 100 parts by mass of Color Index Pigment Green 36. The upper limit is preferably 370 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 200 parts by mass or less. The lower limit is preferably 103 parts by mass or more, more preferably 110 parts by mass or more, and further preferably 120 parts by mass or more.

The coloring composition of the present invention contains 50 to 100 parts by mass of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 in total with respect to 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7. Is preferable. The upper limit is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and further preferably 85 parts by mass or less. The lower limit is preferably 53 parts by mass or more.

The coloring composition of the present invention may contain a green pigment (hereinafter, also referred to as another green pigment) other than the color index pigment green 36 and the color index pigment green 7 as the green pigment. Examples of other green pigments include Color Index Pigment Green 10, 37, 58, 59 and the like. Further, as another green pigment, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. May be further contained. Specific examples of such a halogenated zinc phthalocyanine pigment include the compounds described in International Publication WO2015 / 118720.

The green pigment used in the coloring composition of the present invention preferably contains 50% by mass or more, more preferably 80% by mass or more, and 90% by mass of the color index pigment green 36 and the color index pigment green 7 in total. It is more preferably contained in an amount of% by mass or more. Further, it is preferable that the green pigment does not substantially contain a green pigment (other green pigment) other than the color index pigment green 36 and the color index pigment green 7. The case where the other green pigment is substantially not contained means that the content of the other green pigment is 1% by mass or less, preferably 0.5% by mass or less, preferably 0.1% by mass. It is more preferable that it is as follows, and it is further preferable that it does not contain other green pigments.

The coloring composition of the present invention may contain a yellow pigment (hereinafter, also referred to as another yellow pigment) other than the color index pigment yellow 139 and the color index pigment yellow 150 as the yellow pigment. Other yellow pigments include Color Index 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 , 129,137,138,147,148,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176 , 177,179,180,181,182,185,187,188,193,194,199,213,214 and the like.

The yellow pigment used in the coloring composition of the present invention preferably contains 50% by mass or more, more preferably 80% by mass or more, and 90% by mass of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 in total. It is more preferably contained in an amount of% by mass or more. Further, it is preferable that the yellow pigment does not substantially contain a yellow pigment (other yellow pigment) other than the color index pigment yellow 139 and the color index pigment yellow 150. The case where the other yellow pigment is substantially not contained means that the content of the other yellow pigment is 1% by mass or less, preferably 0.5% by mass or less, preferably 0.1% by mass. It is more preferable that it is as follows, and it is further preferable that it does not contain other yellow pigments.

The average primary particle size of the green pigment and the yellow pigment used in the coloring composition of the present invention is preferably 1 μm or less, more preferably 500 nm or less, further preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less. .. The lower limit is not particularly limited, but is preferably 10 nm or more from the viewpoint of handling. Unless otherwise specified, the ratio (Mv / Mn) of the volume average particle size (Mv) to the number average particle size (Mn) is used as an index indicating the monodispersity of the particles in the present invention. The monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1. 5 is particularly preferable. In the present invention, the average primary particle diameter of the pigment is the diameter equivalent to a circle obtained from the image observed with a transmission electron microscope, and is the average value of 500 of them.

A conventionally known method can be used as the method for refining the pigment. For example, the breakdown method and the build-up method can be mentioned. Examples of the former (breakdown method) include the bead mill method and the salt milling method. For example, the explanation given in the section "Mechanical crushing" on page 12-21 of the Journal of the Imaging Society of Japan, Vol. 45, No. 5 (2006) can be referred to. Further, regarding the salt milling method, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-046629 can be referred to, and these contents are incorporated in the present specification. The latter (build-up method) is also referred to as a reprecipitation method, and for example, JP-A-2011-026452, JP-A-2011-012214, JP-A-2011-001501, JP-A-2010-235895, and the like. JP-A-2010-2091, JP-A-2010-209160, and the like can be referred to, and the contents thereof are incorporated in the present specification.

The coloring composition of the present invention preferably contains 50 to 100 parts by mass of a yellow pigment with respect to 100 parts by mass of a green pigment. The upper limit is preferably 95 parts by mass or less, more preferably 93 parts by mass or less, and further preferably 91 parts by mass or less. The lower limit is preferably 51 parts by mass or more, more preferably 52 parts by mass or more, and further preferably 53 parts by mass or more. According to this aspect, it is easy to form a cured film suitable for green pixels having spectral characteristics excellent in color separation from red and blue. Furthermore, it is easy to form a pattern having a higher rectangularity.

The coloring composition of the present invention preferably contains a total of 35 to 50% by mass of the green pigment and the yellow pigment with respect to the total solid content of the coloring composition. The upper limit is preferably 48% by mass or less, more preferably 46% by mass or less, and further preferably 44% by mass or less. The lower limit is preferably 37% by mass or more, more preferably 39% by mass or more, and further preferably 41% by mass or more.

The coloring composition of the present invention has a total of 35 to 50 mass of Color Index Pigment Green 36, Color Index Pigment Green 7, Color Index Pigment Yellow 139, and Color Index Pigment Yellow 150 with respect to the total solid content of the coloring composition. % Is preferably contained. The upper limit is preferably 48% by mass or less, more preferably 46% by mass or less, and further preferably 44% by mass or less. The lower limit is preferably 37% by mass or more, more preferably 39% by mass or more, and further preferably 41% by mass or more. According to this aspect, it is easy to form a cured film suitable for green pixels having spectral characteristics excellent in color separation from red and blue. In particular, it is easy to form a cured film having high transmittance of light in the wavelength range of 500 to 550 nm and high shielding property against light in the wavelength range of 400 to 470 nm and light in the wavelength range of 600 to 700 nm. Furthermore, it is easy to form a pattern having a higher rectangularity.

In the coloring composition of the present invention, the total amount of the color index pigment green 36, the color index pigment green 7, the color index pigment yellow 139 and the color index pigment yellow 150 is 85 with respect to the total amount of the colorant contained in the coloring composition. Mass% or more is preferable, 90% by mass or more is more preferable, and 95% by mass or more is further preferable. Here, the total amount of the colorant means the total amount of the green pigment, the yellow pigment and the other colorants described later when the colorant other than the green pigment and the yellow pigment (other colorants described later) is further contained. To tell.

<< Other colorants >>
The coloring composition of the present invention may further contain a coloring agent other than the green pigment and the yellow pigment (hereinafter, also referred to as other coloring agents). The other colorants may be either dyes or pigments, or both may be used in combination. Examples of the pigment include various conventionally known inorganic pigments or organic pigments. Further, considering that high transmittance is preferable regardless of whether it is an inorganic pigment or an organic pigment, the average primary particle size of the pigment as another colorant is preferably small. Considering the handleability, the average primary particle size of the pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Further, black pigments such as carbon black and titanium black, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals are mentioned. You can also.

Examples of the organic pigment include the following organic pigments.
Color Index 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 mag (above, orange pigment),
Color Index 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, 184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279, etc. (Above, red pigment),
Color Index Pigment Violet 1,19,23,27,32,37,42, etc. (above, purple pigment),
Color Index Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,60,64,66,79,80, etc. (above, blue pigment) ..
Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraphs 0047 of JP2011-157478A.

The dye is not particularly limited, and known dyes can be used. The chemical structures include pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, and pyrrolopyrazole azomethine. Dyes such as xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used. Further, the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, and the azo compound described in JP-A-2011-145540 can also be preferably used. Further, as the yellow dye, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-54339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-262228 can also be used.

Moreover, you may use a dye multimer as another colorant. The dye multimer is preferably a dye that is used by dissolving it in a solvent, but may form particles. When the dye multimer is a particle, the dye multimer is used by dispersing it in a solvent or the like. The pigment multimer in the particle state can be obtained, for example, by emulsion polymerization. Examples of the dye multimer in the particle state include compounds described in JP-A-2015-214682. Further, as the dye multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742 and the like can also be used. ..

When the coloring composition of the present invention contains another coloring agent, the content of the other coloring agent is preferably 10% by mass or less with respect to the total solid content of the coloring composition. The upper limit is preferably 7% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more. The other colorants may be one kind or two or more kinds. When two or more types are included, it is preferable that the total is within the above range.
It is also preferable that the coloring composition of the present invention does not substantially contain other coloring agents. The term "substantially free of other colorants" means that the amount is preferably 1 part by mass or less, more preferably 0.1 part by mass or less, based on 100 parts by mass of the total of the green pigment and the yellow pigment. , 0.01 part by mass or less, and particularly preferably not containing other colorants.

<< Polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound 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 the ethylenically unsaturated bonding group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. 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 a monomer, a prepolymer or an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 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, and 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, and the ethylenically unsaturated bond group. It is more preferable that the compound contains 3 to 6 compounds. Further, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.

Specific examples of the polymerizable compound are described in paragraphs 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-29760, and paragraphs 0254 to 0257 of JP2008-292970. Compounds are mentioned and these contents are incorporated herein.

式（Ｍ－１１）

In the present invention, the polymerizable compound is preferably a compound having an alkyleneoxy group. By using such a compound, it is possible to impart appropriate flexibility to the film. Further, the hydrophilicity of the film can be enhanced, the solubility in the developing solution in the unexposed portion can be enhanced, and the generation of the developing residue can be suppressed. The polymerizable compound having an alkyleneoxy group is preferably a compound represented by the following formula (M-10) and / or the following formula (M-11), and the compound represented by the following formula (M-11). Is more preferable.
Equation (M-10)

Equation (M-11)

In equations (M-10) and (M-11), E is independently-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-. Represents, and y independently represents an integer of 1 to 10. X ¹ and X ² each independently represent a (meth) acryloyl group, a hydrogen atom or -L-CO ₂ H, where L is -CH _2- , -C (= O)-, -O- or these. Represents a group consisting of a combination of. In the formula (M-10), the total number of (meth) acryloyl groups is 3 or 4, and m independently represents an integer of 0 to 10, and the total of each m is an integer of 1 to 40. In formula (M-11), the total number of (meth) acryloyl groups is 5 or 6, where n independently represents an integer of 0 to 10, and the total of each n is an integer of 1 to 60. )

In the formula (M-10),-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O) has a form in which the terminal on the oxygen atom side is bonded to X ¹ . preferable. Further, y is preferably an integer of 1 to 8 independently, and more preferably an integer of 1 to 5. Further, X ¹ is preferably a (meth) acryloyl group. For m, an integer of 0 to 8 is preferable, and an integer of 0 to 4 is more preferable. The total of each m is preferably an integer of 4 to 20.

In the formula (M-11),-((CH ₂ ) _y CH ₂ O)-or ((CH ₂ ) _y CH (CH ₃ ) O)-has a form in which the terminal on the oxygen atom side is bonded to X ² . preferable. y is preferably an integer of 1 to 8 independently, and more preferably an integer of 1 to 5. X ² is preferably a (meth) acryloyl group. n is preferably an integer of 0 to 8, more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 6 to 30.

Specific examples of the polymerizable compound having an alkyleneoxy group include SR-494 (manufactured by Sartmer) and KAYARAD TPA-330 (Nippon Kayaku Co., Ltd.), which are tetrafunctional (meth) acrylates having four ethyleneoxy groups. ), Aronix M-350 (manufactured by Toagosei Co., Ltd.) and the like. Further, a compound having the following structure is also given as a specific example.

Examples of the polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.). ), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku) NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and the structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. Compounds (eg, SR454, SR499, commercially available from Sartmer) and the like can also be used. Examples of the compound having an ethylenically unsaturated bond group include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and ethyleneoxy isocyanurate. It is also preferable to use a trifunctional (meth) acrylate compound such as a modified tri (meth) acrylate or pentaerythritol tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.

As the polymerizable compound, a compound having an acid group can also be used. By using such a compound, the generation of development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable. Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).

When the polymerizable compound is a compound having an acid group, the acid value of the polymerizable compound is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.

It is also a preferred embodiment that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

Examples of the polymerizable compound include urethane acrylates as described in JP-A-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Further, a compound having an ethylenically unsaturated bond group having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. It is also preferable to use. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and UA. -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

The content of the polymerizable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the coloring composition. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, further preferably 40% by mass or less. The polymerizable compound may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total is within the above range.

When the coloring composition contains a polymerizable compound having an alkyleneoxy group, it is preferable to contain 10% by mass or more of the polymerizable compound having an alkyleneoxy group with respect to the total mass of the polymerizable compound, and 20% by mass or more. It is more preferable to contain it, and it is further preferable to contain it in an amount of 30% by mass or more. According to this aspect, the generation of development residue can be suppressed more effectively.

<< Photopolymerization Initiator >>
The coloring composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be a compound that produces an active radical by causing some action with a photoexcited sensitizer.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and the like. Examples thereof include thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. Dimer, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred, oxime compounds, α-hydroxyketone compounds, α- A compound selected from an aminoketone compound and an acylphosphine compound is more preferable, and an oxime compound is further preferable. As the photopolymerization initiator, the description in paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.

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

As the oxime compound, for example, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyimiminopentane-3-3. On, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Examples thereof include carbonyloxyimino-1-phenylpropane-1-one.

Examples of the oxime compound include J. C. S. Perkin II (1979, pp. 1653-1660), J. Mol. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-66385, JP-A-2000-80068, JP-A-2004. Compounds and the like described in Japanese Patent Application Laid-Open No. 534797 and Japanese Patent Application Laid-Open No. 2006-342166 can also be used. As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF) are also preferably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd. (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)), ADEKA ARC , ADEKA PTOMER N-1919 (photopolymerization initiator 2 described in JP-A-2012-14052) (above, manufactured by ADEKA Corporation) can be used.

Further, as an oxime compound other than the above, the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of the carbazole ring, and the compound described in US Pat. No. 6,626,957 in which a heterosubstituted group is introduced into a benzophenone moiety. , The compound described in JP-A-2010-15025 and US Patent Publication No. 2009-292039, the keto-oxime compound described in International Publication WO2009 / 131189, the same as the triazine skeleton and the oxime skeleton. Even if the compound described in US Pat. No. 5,556,910, which is contained in the molecule, or the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, is used. good. Preferably, for example, paragraph numbers 0274 to 0306 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

An oxime compound having a fluorene ring can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein. An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator. Specific examples thereof include compounds OE-01 to OE-75 described in International Publication No. WO2015 / 036910.

An oxime compound having a fluorine atom can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like can be mentioned. This content is incorporated herein.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. 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 paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466, patents 4223071. Examples thereof include the compounds described in paragraphs 0007 to 0025 of the publication, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation), and the like.

Specific examples of the oxime compound 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 region of 350 nm to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm. Further, the oxime compound is preferably a compound having a high absorbance at 365 nm and 405 nm.

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, from the viewpoint of sensitivity. It is particularly preferably 000. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the coloring composition. When the content of the photopolymerization initiator is in the above range, good sensitivity and good pattern forming property can be obtained. The coloring composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators. When two or more photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<< Solvent >>
The coloring composition of the present invention contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition.

Examples of the organic solvent include the following organic solvents. Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyoxyacetate. (For example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionate. Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate) (Ethyl, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate) , 2-Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2- Ethyl methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , 2-oxobutanoate methyl, 2-oxobutanoate ethyl and the like. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. As the aromatic hydrocarbons, for example, toluene, xylene and the like are preferably mentioned. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. Million) or less, 10 mass ppm or less, or 1 mass ppm or less).

The organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate are particularly preferable. , 2-Heptanone, Cyclohexanone, Ethylcarbitol Acetate, Butyl Carbitol Acetate, Propylene Glycol Monomethyl Ether, and Propylene Glycol Monomethyl Ether Acetate.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide. Further, it is preferable to use an organic solvent having a low metal content, and for example, the metal content of the organic solvent is preferably 10 mass ppb (parts per parts) or less. If necessary, an organic solvent having a metal content of mass ppt (parts per tension) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, 2015). November 13th).

The content of the solvent is preferably an amount such that the total solid content of the coloring composition is 5 to 80% by mass. The lower limit is preferably 10% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.

<< UV absorber >>
The coloring composition of the present invention preferably contains an ultraviolet absorber. By incorporating an ultraviolet absorber into the coloring composition of the present invention, it is easy to form a highly rectangular pattern.

As the ultraviolet absorber, a conjugated diene compound, an aminobutadiene compound, a methyldibenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound and the like can be used. For details thereof, the description of paragraph numbers 0052 to 0072 of JP2012-208374A and paragraph numbers 0317 to 0334 of JP2013-68814 can be referred to, and these contents are incorporated in the present specification. Examples of commercially available products of ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Further, as the benzotriazole compound, the MYUA series (The Chemical Daily, February 1, 2016) manufactured by Miyoshi Oil & Fat may be used. Among them, as the ultraviolet absorber, a conjugated diene compound, a methyldibenzoyl compound, a coumarin compound and a benzotriazole compound are preferable, and a conjugated diene compound and a methyldibenzoyl compound are more preferable because the molar absorption coefficient at a wavelength of 365 nm is high. ..

The conjugated diene compound is preferably a compound represented by the following formula (UV-1).

In the formula (UV-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² are They may be the same or different from each other, but they do not represent hydrogen atoms at the same time.
R ¹ and R ² may form a cyclic amino group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include a piperidino group, a morpholino group, a pyrrolidine group, a hexahydroazepino group, a piperazino group and the like.
R ¹ and R ² are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms.
R ³ and R ⁴ represent electron-withdrawing groups. R ³ and R ⁴ are preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group and a sulfamoyl group, preferably an acyl group and a carbamoyl group. Groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, cyano groups, alkylsulfonyl groups, arylsulfonyl groups, sulfonyloxy groups and sulfamoyl groups are preferred. Further, R ³ and R ⁴ may be bonded to each other to form a cyclic electron-withdrawing group. Examples of the cyclic electron-withdrawing group formed by bonding R ³ and R ⁴ to each other include a 6-membered ring containing two carbonyl groups.
At least one of the above R ¹ , R ² , R ³ and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.

The description of the substituent of the UV absorber represented by the formula (UV-1) is described in paragraphs 0024 to 0033 of WO2009 / 123109 (corresponding US patent application publication 2011/0039195, paragraph number 0040). ~ 0059) can be taken into consideration, and these contents are incorporated in the present specification. Specific examples of the ultraviolet absorber represented by the formula (UV-1) include the following compounds. In addition, preferred specific examples of the compound represented by the formula (UV-1) are paragraph numbers 0034 to 0037 of International Publication WO2009 / 123109 (paragraph number 0060 of the corresponding US Patent Application Publication No. 2011/0039195. The description of the exemplary compounds (1) to (14) of)) can be taken into consideration, and these contents are incorporated in the present specification. Examples of commercially available products of the ultraviolet absorber represented by the formula (UV-1) include UV503 (manufactured by Daito Kagaku Co., Ltd.).

As the methyldibenzoyl compound, a compound represented by the following formula (UV-2) is preferable.

In formula (UV-2), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0-4.

The substituents represented by R ¹⁰¹ and R ¹⁰² are halogen atom, cyano group, nitro group, alkyl group, aryl group, heteroaryl group, alkoxy group, allyloxy group, heteroallyloxy group, alkylthio group, arylthio group and heteroarylthio. Group, -NR ^U1 R ^U2 , -COR ^U3 , -COOR ^U4 , -OCOR ^U5 , -NHCOR ^U6 , -CONR ^U7 R ^U8 , -NHCONR ^U9 R ^U10 , -NHCOOR ^U11 , -SO ₂ R ^U12 , -SO ₂ OR Examples include ^U13 , -NHSO ₂ R ^U14 or -SO ₂ NR ^U15 R ^U16 . Each of ^{RU1 to RU16 independently} represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.

It is preferable that the substituents represented by R ¹⁰¹ and R ¹⁰² are independently alkyl groups or alkoxy groups, respectively. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10. Examples of the alkyl group include linear, branched and cyclic, and linear or branched is preferable, and branching is more preferable. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 10. The alkoxy group is preferably linear or branched, more preferably branched.

In the formula (UV-2), a combination in which one of R ¹⁰¹ and R ¹⁰² is an alkyl group and the other is an alkoxy group is preferable.

m1 and m2 independently represent 0 to 4, respectively. M1 and m2 are each independently preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.

Specific examples of the compound represented by the formula (UV-2) include avobenzone.

The content of the ultraviolet absorber in the coloring composition of the present invention is preferably 0.5 to 8% by mass with respect to the total solid content of the coloring composition. The upper limit is preferably 7% by mass or less, more preferably 6% by mass or less, and further preferably 5% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. When the content of the ultraviolet absorber is within the above range, it is easy to form a highly rectangular pattern.

<< Resin >>
The coloring composition of the present invention may contain a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like in a composition or for a binder. The resin mainly used for dispersing pigments and the like is also referred to as a dispersant. However, such use of the resin is an example, and it can be used for purposes other than such use.

The weight average molecular weight (Mw) of the resin is preferably 2,000 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 3,000 or more, more preferably 5,000 or more.

The coloring composition of the present invention preferably contains a resin as a dispersant. Examples of the dispersant include polymer dispersants [for example, polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth). Acrylic copolymer, naphthalene sulfonic acid formarin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine and the like can be mentioned. The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure. The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor portion on the pigment surface can be mentioned as preferable structures. Further, the dispersant described in paragraphs 0028 to 0124 of JP-A-2011-070156 and the dispersant described in JP-A-2007-277514 are also preferably used. These contents are incorporated in the present specification.

Examples of the resin as the dispersant include an acidic dispersant and a basic dispersant, and it is preferable that the resin contains at least an acidic dispersant. The acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acid dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially acid. A resin consisting only of a group is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 5 to 105 mgKOH / g, more preferably 40 to 105 mgKOH / g, even more preferably 50 to 105 mgKOH / g, and particularly preferably 60 to 105 mgKOH / g. Examples of the acidic dispersant (acidic resin) include resins having the following structures. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.

In the present invention, it is preferable to use a resin containing a repeating unit having a nitrogen atom in the main chain. When the coloring composition contains such a resin, the dispersibility of the pigment in the coloring composition can be further enhanced. A resin containing a repeating unit having a nitrogen atom in the main chain can be preferably used as a dispersant. Resins containing repeating units having a nitrogen atom in the main chain include poly (lower alkyleneimine) -based repeating units, polyallylamine-based repeating units, polydialylamine-based repeating units, metaxylene diamine-epichlorohydrin polycondensate-based repeating units, and polyvinyl. It preferably contains at least one repeating unit selected from amine-based repeating units.

As the resin containing a repeating unit having a nitrogen atom in the main chain, a repeating unit having a partial structure X having a functional group of pKa14 or less and a side chain containing an oligomer chain or a polymer chain Y having 40 to 10,000 atoms are included. It is preferable that the resin has a repeating unit.

The resin containing a repeating unit having a nitrogen atom in the main chain is, for example, a repeating unit represented by the formula (I-1), a repeating unit represented by the formula (I-2), and / or a repeating unit represented by the formula (I-2). It is preferable to use a resin containing the repeating unit represented by -2a).

Ｒ^１及びＲ^２は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１～６が好ましい）を表す。ａは、各々独立に、１～５の整数を表す。＊は繰り返し単位間の連結部を表す。
Ｒ^８及びＲ^９はＲ^１と同義の基である。
Ｌは単結合、アルキレン基（炭素数１～６が好ましい）、アルケニレン基（炭素数２～６が好ましい）、アリーレン基（炭素数６～２４が好ましい）、ヘテロアリーレン基（炭素数１～６が好ましい）、イミノ基（炭素数０～６が好ましい）、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基である。なかでも、単結合もしくは－ＣＲ^５Ｒ^６－ＮＲ^７－（イミノ基がＸもしくはＹの方になる）であることが好ましい。ここで、Ｒ^５、Ｒ^６は各々独立に、水素原子、ハロゲン原子、アルキル基（炭素数１～６が好ましい）を表す。Ｒ^７は水素原子または炭素数１～６のアルキル基を表す。
Ｌ^ａはＣＲ^８ＣＲ^９とＮとともに環構造を形成する構造部位であり、ＣＲ^８ＣＲ^９の炭素原子と合わせて炭素数３～７の非芳香族複素環を形成する構造部位であることが好ましい。さらに好ましくは、ＣＲ^８ＣＲ^９の炭素原子及びＮ（窒素原子）を合わせて５～７員の非芳香族複素環を形成する構造部位であり、より好ましくは５員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。この構造部位はさらにアルキル基等の置換基を有していてもよい。
ＸはｐＫａ１４以下の官能基を有する基を表す。
Ｙは原子数４０～１０，０００の側鎖を表す。

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a independently represents an integer of 1 to 5. * Represents the connection between repeating units.
R ⁸ and R ⁹ are synonymous with R ¹ .
L is a single bond, an alkylene group (preferably 1 to 6 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), an arylene group (preferably 6 to 24 carbon atoms), and a heteroarylene group (preferably 1 to 6 carbon atoms). (Preferably), imino group (preferably 0 to 6 carbon atoms), ether group, thioether group, carbonyl group, or a linking group according to a combination thereof. Among them, a single bond or -CR ⁵ R ⁶ -NR ^7- (the imino group is X or Y) is preferable. Here, R ⁵ and R ⁶ independently represent a hydrogen atom, a halogen atom, and an alkyl group (preferably having 1 to 6 carbon atoms). R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
La is ^a structural site that forms a ring structure together with CR ⁸ CR ⁹ and N, and may be a structural site that forms a non-aromatic heterocycle having 3 to 7 carbon atoms together with the carbon atom of CR ⁸ CR ⁹ . preferable. More preferably, it is a structural moiety that combines the carbon atom and N (nitrogen atom) of CR ⁸ CR ⁹ to form a 5- to 7-membered non-aromatic heterocycle, and more preferably a 5-membered non-aromatic heterocycle. It is a structural site to be formed, and it is particularly preferable that it is a structural site to form pyrrolidine. This structural site may further have a substituent such as an alkyl group.
X represents a group having a functional group of pKa14 or less.
Y represents a side chain having 40 to 10,000 atoms.

The resin containing a repeating unit having a nitrogen atom in the main chain may further contain a repeating unit represented by the formula (I-3), the formula (I-4), and the formula (I-5).

R ¹ , R ² , R ⁸ , R ⁹ , L, La, a and * are synonymous with the provisions in formulas (I-1), (I-2) and (I-2a). Ya represents a side chain having an anionic group and having 40 to 10,000 atoms. In the repeating unit represented by the formula (I-3), an oligomer or a polymer having a group that reacts with an amine to form a salt is added to a resin having a primary or secondary amino group in the main chain to react. It is possible to form by.

Regarding the resin containing a repeating unit having a nitrogen atom in the main chain, the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and the above contents are incorporated in the present specification. Specific examples of the resin containing a nitrogen atom in the main chain include the following. Further, the resin described in paragraph numbers 0168 to 0174 of JP2012-255128A can be used.

It is also preferable that the coloring composition of the present invention contains a resin containing a repeating unit having a graft chain in the side chain (hereinafter, also referred to as a graft resin). According to this aspect, the dispersibility of the pigment can be further improved. The graft resin can be preferably used as a dispersant. Here, the graft chain means a polymer chain that branches and extends from the main chain of a repeating unit. The length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, and the dispersibility of the pigment or the like can be improved. In the graft chain, the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, the number of atoms excluding hydrogen atoms is more preferably 50 to 2000, and the number of atoms excluding hydrogen atoms is 60 to. It is more preferably 500.

The graft chain preferably contains at least one structure selected from polyester chains, polyether chains, poly (meth) acrylic chains, polyurethane chains, polyurea chains and polyamide chains, preferably polyester chains, polyether chains and poly (meth) chains. ) It is more preferable to include at least one structure selected from acrylic chains, and even more preferably to contain polyester chains.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving the dispersibility of pigments and the like. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.

Examples of the graft resin include resins having the following structures. Further, for the details of the graft resin, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the contents thereof are incorporated in the present specification.

As the resin as a dispersant, a commercially available product can also be used. For example, Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) and the like can be mentioned. Further, the product described in paragraph No. 0129 of JP2012-137564A can also be used as a dispersant. 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 coloring composition of the present invention preferably contains an alkali-soluble resin as the resin. When the coloring composition contains an alkali-soluble resin, the developability is improved and the generation of development residues can be effectively suppressed. The alkali-soluble resin can also be used as a dispersant.

The alkali-soluble resin can be appropriately selected from the resins having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group and the like, and a carboxyl group is preferable. The type of acid group contained in the alkali-soluble resin may be only one type or two or more types.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 to 100,000. The number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.

As the alkali-soluble resin, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable from the viewpoint of heat resistance. Further, from the viewpoint of controllability of developability, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable.

The alkali-soluble resin is preferably a polymer containing a repeating unit having an acid group in the side chain, and more preferably a polymer containing a repeating unit having a carboxyl group in the side chain. For example, a copolymer having a repeating unit derived from a monomer such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinyl benzoic acid, partially esterified maleic acid, etc. Examples thereof include an alkali-soluble phenol form such as a novolak type resin, an acidic cellulose derivative having a carboxyl group in the side chain, and a polymer in which an acid anhydride is added to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, trill (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Can be mentioned. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltolune, acrylonitrile, vinylacetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like. In addition, examples of other monomers include N-position substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide. The other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.

Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multiplex copolymer composed of / (meth) acrylic acid / other monomer can be preferably used. Further, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate with another monomer, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / described in JP-A-7-140654. Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethylmethacrylate macromonomer / benzylmethacrylate / methacrylic acid copolymer, 2-hydroxyethylmethacrylate / polystyrene macromonomer / methylmethacrylate / methacrylic acid copolymer, 2-Hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used. Further, as a commercially available product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) or the like can be used.

As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group can also be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. The alkali-soluble resin having a polymerizable group is preferably a resin containing a repeating unit having a polymerizable group in the side chain and a repeating unit having an acid group in the side chain. Specific examples of the alkali-soluble resin having a polymerizable group include resins having the following structures. In the following structural formula, Me represents a methyl group. Commercially available products of alkali-soluble resins having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, Diamond Shamrock Co., Ltd.), and Viscort R-264. , KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebeclyl3800 (manufactured by Daicel UCB Co., Ltd.), Examples thereof include acrylic cure RD-F8 (manufactured by Nippon Catalyst Co., Ltd.) and DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.).

The alkali-soluble resin is at least one compound selected from the compound represented by the following formula (ED1) and the compound represented by the formula (1) of JP-A-2010-168539 (hereinafter, these compounds are referred to as "ether dimer". It is also preferable to include a polymer obtained by polymerizing a monomer component containing).

In the formula (ED1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.

As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the content thereof is incorporated in the present specification. The ether dimer may be only one kind or two or more kinds.

式（Ｘ）において、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。 The alkali-soluble resin may contain a repeating unit derived from the 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, and R ₃ represents a hydrogen atom or a benzene ring and may contain 1 to 20 carbon atoms. Represents the alkyl group of. n represents an integer from 1 to 15.

In the above formula (X), the alkylene group of _R2 preferably has 2 to 3 carbon atoms. Further, the number of carbon atoms of the alkyl group of R3 is preferably ₁ to 10. The alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

For the alkali-soluble resin, the description in paragraph numbers 0558 to 0571 of JP2012-208494A (paragraph numbers 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof are described in the present specification. Incorporated into the book.
Further, the alkali-soluble resin is the copolymer (B) described in paragraphs 0029 to 0063 of JP-A-2012-32767 and the alkali-soluble resin used in Examples, paragraphs of JP-A-2012-208474. Binder resins described in Nos. 0088 to 0998 and binder resins used in Examples, binder resins described in paragraphs Nos. 0022 to 0032 of JP2012-137531A, and binder resins used in Examples. The binder resin described in paragraphs 0132 to 0143 of Japanese Patent Application Laid-Open No. 2013-024934 and the binder resin used in Examples, paragraph numbers 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and the binder used in Examples. Resins, binder resins described in paragraphs 0030 to 0072 of JP2012-032770A can also be used, and the contents thereof are incorporated in the present specification.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, further preferably 150 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less.

The content of the resin is preferably 1 to 80% by mass with respect to the total solid content of the coloring composition. The lower limit is more preferably 10% by mass or more, further preferably 20% by mass or more. The upper limit is more preferably 60% by mass or less, further preferably 40% by mass or less. The coloring composition of the present invention may contain only one kind of resin, or may contain two or more kinds of resins. When two or more types are included, it is preferable that the total of them is in the above range.
The content of the resin is preferably 100 to 250 parts by mass with respect to 100 parts by mass of the polymerizable compound. The lower limit is more preferably 130 parts by mass or more, and further preferably 160 parts by mass or more. The upper limit is more preferably 230 parts by mass or less, and further preferably 200 parts by mass or less. The coloring composition of the present invention may contain only one kind of resin, or may contain two or more kinds of resins. When two or more types are included, it is preferable that the total of them is in the above range.

<< Compounds with epoxy groups >>
The coloring composition of the present invention can contain a compound having an epoxy group (hereinafter, also referred to as an epoxy compound). The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The lower limit of the epoxy group is more preferably two or more. The upper limit of the epoxy group may be, for example, 10 or less, or 5 or less.

The epoxy equivalent (= molecular weight of the epoxy compound / number of epoxy groups) is preferably 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g / equivalent. More preferred.

The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, further preferably 5000 or less, and even more preferably 3000 or less.

Examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP2014-0435556, and paragraph numbers 0083 to 0092 of JP2014-089408. Compounds can also be used. These contents are incorporated in the present specification.

When the coloring composition of the present invention contains an epoxy compound, the content of the epoxy compound is preferably 0.1 to 40% by mass with respect to the total solid content of the coloring composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, further preferably 20% by mass or less. The epoxy compound may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total is within the above range.
The coloring composition of the present invention may also contain substantially no epoxy compound. The fact that the epoxy compound is not substantially contained means that the content of the epoxy compound is preferably 0.05% by mass or less, and preferably 0.01% by mass or less, based on the total solid content of the coloring composition. It is more preferable, and it is more preferable that it is not contained.

<< Curing Accelerator >>
The coloring composition of the present invention may contain a curing accelerator for the purpose of improving the hardness of the pattern and for the purpose of lowering the curing temperature. Examples of the curing accelerator include thiol compounds and the like.

（式（Ｔ１）中、ｎは２～４の整数を表し、Ｌは２～４価の連結基を表す。） Examples of the thiol compound include a polyfunctional thiol compound having two or more mercapto groups in the molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol compound, and more preferably a compound having a structure represented by the following formula (T1).
Equation (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valences.)

In the above formula (T1), L is preferably an aliphatic group having 2 to 12 carbon atoms. In the above formula (T1), it is more preferable that n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and the compound represented by the formula (T2) is preferable. One type of thiol compound may be used, or two or more types may be used in combination.

Further, the curing accelerator is a methylol-based compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-34963), amines, phosphonium salt, amidin salt, amide compound (for example, above, for example. Hardeners described in paragraph No. 0186 of JP2013-41165A, base generators (eg, ionic compounds described in JP2014-55114), isocyanate compounds (eg, JP2012-150180). Japanese Patent Laid-Open No. 0071), alkoxysilane compound (for example, alkoxysilane compound having an epoxy group described in JP-A-2011-253504), onium salt compound (eg, JP-A-2015-34963). A compound exemplified as an acid generator in paragraph No. 0216, a compound described in JP-A-2009-180949) and the like can also be used.

When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass, preferably 0.8 to 6% by mass, based on the total solid content of the coloring composition. .4% by mass is more preferable.

<< Pigment derivative >>
The coloring composition of the present invention preferably contains a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is replaced with an acid group, a basic group or a phthalimide methyl group.

The chromogens constituting the pigment derivative include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthracinone skeleton, quinacridone skeleton, dioxazine skeleton, and perinone skeleton. Skeletons, perylene-based skeletons, thioindigo-based skeletons, isoindolin-based skeletons, isoindolinone-based skeletons, quinophthalone-based skeletons, slene-based skeletons, metal complex-based skeletons, etc. Pyrrolopyrrole-based skeletons, azo-based skeletons, quinophthalone-based skeletons, isoindrin-based skeletons and phthalocyanine-based skeletons are preferable, and azo-based skeletons and benzoimidazolone-based skeletons are more preferable. As the acid group of the pigment derivative, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable. For details of the pigment derivative, the description in paragraphs 0059 to 0086 of JP-A-2015-102612 can be referred to, and the content thereof is incorporated in the present specification.

When the coloring composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination.

<< Surfactant >>
The coloring composition of the present invention preferably contains a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used to further improve the coatability. Fluorosurfactants are preferred because they can.

By containing a fluorine-based surfactant in the coloring composition of the present invention, the liquid characteristics when prepared as a coating liquid can be improved, and the uniformity of the coating thickness can be further improved. That is, when a film is formed by using a coating liquid to which a coloring composition containing a fluorine-based surfactant is applied, the interfacial tension on the surface of the coating film is reduced and the uniformity of drying is improved. Therefore, it is possible to more preferably form a film with less coating unevenness.

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

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (above, DIC Corporation). , Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC 383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP2011-132503 can also be used. A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include the compounds described in JP-A-2011-89090.

The fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved when heat is applied and the fluorine atom volatilizes can also be preferably used. .. Examples of such a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS. -21 can be mentioned.

上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、例えば、１４，０００である。 The fluorine-based surfactant 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) (meth). ) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention. In the following formula,% indicating the ratio of the repeating unit is mol%.

The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, for example 14,000.

As the fluorine-based surfactant, a fluorine-containing polymer having a group having an ethylenically unsaturated bond in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965. Examples of commercially available products include Megafuck RS-101, RS-102, RS-718-K, RS-72-K manufactured by DIC Corporation.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. 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) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

Examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the coloring composition. Only one type of surfactant may be used, or two or more types may be combined. When two or more types are included, the total amount is preferably in the above range.

<< Silane Coupling Agent >>
The coloring composition of the present invention can contain a silane coupling agent. In the present invention, the 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 linked to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like.

The silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styryl group, a methacrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. A silane compound having and is preferable. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and N-β-aminoethyl-γ-aminopropyltri. Methoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-602), γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBM-903), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503), 3- Examples thereof include glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) and compounds having the following structures. In the following structural formula, Et represents an ethyl group. For details of the silane coupling agent, the description in paragraphs 0155 to 0158 of JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification.

When the coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass, preferably 0.01 to 20% by mass, based on the total solid content of the coloring composition. 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. The coloring composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds of silane coupling agents. When two or more kinds of silane coupling agents are contained, it is preferable that the total amount thereof is within the above range.

<< Polymerization inhibitor >>
The coloring composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, first cerium salt, etc.).
When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the coloring composition. The coloring composition of the present invention may contain only one kind of polymerization inhibitor, or may contain two or more kinds of polymerization inhibitors. When two or more types are included, it is preferable that the total amount thereof is within the above range.

<< Other additives >>
Various additives such as fillers, adhesion promoters, antioxidants, antiaggregating agents and the like can be added to the coloring composition of the present invention, if necessary. Examples of these additives include the additives described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated in the present specification. Further, as the antioxidant, for example, a phenol compound, a phosphorus-based compound (for example, the compound described in paragraph No. 0042 of JP-A-2011-90147), a thioether compound and the like can be used. Commercially available products include, for example, the ADEKA stub series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-" manufactured by ADEKA Corporation. 330 etc.). Only one kind of antioxidant may be used, or two or more kinds may be used. The coloring composition of the present invention can contain a sensitizer and a photostabilizer described in paragraph No. 0078 of JP-A-2004-295116, and a thermal polymerization inhibitor described in paragraph No. 1981 of the same publication.

Metallic elements may be contained in the coloring composition depending on the raw materials used, etc., but the content of Group 2 elements (calcium, magnesium, etc.) in the coloring composition is 50% by mass or less from the viewpoint of suppressing the generation of defects. Is preferable, and 0.01 to 10 mass ppm is more preferable. The total amount of the inorganic metal salt in the coloring composition is preferably 100% by mass or less, more preferably 0.5 to 50% by mass.

The water content of the coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

The coloring composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface (flatness, etc.), adjusting the film thickness, and the like. The viscosity value can be appropriately selected as needed, but for example, at 25 ° C., 0.3 mPa · s to 50 mPa · s is preferable, and 0.5 mPa · s to 20 mPa · s is more preferable. As a method for measuring the viscosity, for example, a viscometer RE85L (rotor: 1 ° 34'× R24, measuring range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo is used, and the temperature is adjusted to 25 ° C. Can be measured.

The container for containing the coloring composition of the present invention is not particularly limited, and a known container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and a bottle in which 6 types of resin are composed of 7 layers are used. It is also preferable to use it. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

The coloring composition of the present invention can be preferably used for forming colored pixels (preferably red pixels) in a color filter. For example, it can be preferably used for a solid-state image pickup device such as a CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor), or a color filter for an image display device or the like.

When the coloring composition of the present invention is used as a color filter for a liquid crystal display device, the voltage retention rate of the liquid crystal display element provided with the color filter is preferably 70% or more, more preferably 90% or more. .. Known means for obtaining a high voltage holding ratio can be appropriately incorporated, and typical means include the use of a high-purity material (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition. Can be mentioned. The voltage retention rate can be measured by, for example, the method described in paragraph 0243 of JP2011-008004A, paragraphs 0123 to 0129 of JP2012-224847A.

<Preparation method of coloring composition>
The coloring composition of the present invention can be prepared by mixing the above-mentioned components. In preparing the coloring composition, all the components may be dissolved and / or dispersed in a solvent at the same time to prepare the coloring composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) to prepare a coloring composition. Above all, it is preferable to prepare a coloring composition by mixing the pigment dispersion of the present invention, which will be described later, with other components (for example, a photopolymerization initiator, a polymerizable compound, a solvent, a resin, an ultraviolet absorber, etc.).

Further, it is preferable to include a process of dispersing the pigment in the preparation of the coloring composition. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes 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. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to treat the pigment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industrial application centered on suspension (solid / liquid dispersion system)". The process and disperser described in paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893, "Practical Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the pigment, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

In preparing the coloring composition, it is preferable to filter 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, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density and / or ultra). A filter using a material such as (including a high molecular weight polyolefin resin) can be mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore size of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm.

Further, as the filter, it is also preferable to use a filter using a fiber-shaped filter medium. Examples of the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specific examples of the filter using the fiber-shaped filter medium include filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Loki Techno Co., Ltd. ..

When using filters, different filters may be combined. At that time, the filtration with each filter may be performed only once or twice or more.
For example, filters having different pore diameters may be combined within the above range. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., etc. can do.
Further, the filtration with the first filter may be performed only with the dispersion liquid, and after mixing the other components, the filtration with the second filter may be performed. As the second filter, a filter made of the same material as the first filter can be used.

<Pigment dispersion>
Next, the pigment dispersion liquid of the present invention will be described.
The pigment dispersion of the present invention contains a green pigment, a yellow pigment and a solvent, and contains.
The green pigment comprises at least Color Index Pigment Green 36 and Color Index Pigment Green 7.
The yellow pigment comprises at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.
The mass ratio of the color index pigment green 36 to the color index pigment green 7 is characterized in that the color index pigment green 36: the color index pigment green 7 = 25: 75 to 50:50.

In the pigment dispersion of the present invention, the mass ratio of the color index pigment green 36 to the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50, and 30: 70 to. It is preferably 45:55, more preferably 35:65 to 40:60. When the mass ratio of the two is in the above range, it is possible to form a cured film suitable for green pixels having spectral characteristics excellent in color separation from red and blue.

In the pigment dispersion of the present invention, the mass ratio of the color index pigment yellow 139 and the color index pigment yellow 150 is color index pigment yellow 139: color index pigment yellow 150 = 0.1: 99.9 to 20:80. It is preferably 1:99 to 15:85, more preferably 3:97 to 10:90, and even more preferably 3:97 to 10:90.

The pigment dispersion of the present invention preferably contains 0.05 to 20 parts by mass of Color Index Pigment Yellow 139 with respect to a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. The lower limit is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2.0 parts by mass or more.

The pigment dispersion of the present invention preferably contains 0.1 to 80 parts by mass of Color Index Pigment Yellow 139 with respect to 100 parts by mass of Color Index Pigment Green 36. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less. The lower limit is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more.

The pigment dispersion of the present invention preferably contains 49.95 to 99.9 parts by mass of Color Index Pigment Yellow 150 with respect to a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7. The upper limit is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and further preferably 85 parts by mass or less. The lower limit is preferably 50 parts by mass or more, and more preferably 51 parts by mass or more.

The pigment dispersion of the present invention preferably contains 99.9 to 399.6 parts by mass of Color Index Pigment Yellow 150 with respect to 100 parts by mass of Color Index Pigment Green 36. The upper limit is preferably 370 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 200 parts by mass or less. The lower limit is preferably 103 parts by mass or more, more preferably 110 parts by mass or more, and further preferably 120 parts by mass or more.

The pigment dispersion of the present invention contains 50 to 100 parts by mass of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 in total with respect to 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7. Is preferable. The upper limit is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and further preferably 85 parts by mass or less. The lower limit is preferably 53 parts by mass or more.

The pigment dispersion liquid of the present invention may further contain a green pigment (other green pigment) other than the color index pigment green 36 and the color index pigment green 7 as a green pigment. The green pigment used in the pigment dispersion of the present invention preferably contains the color index pigment green 36 and the color index pigment green 7 in a total amount of 50% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. It is more preferably contained in an amount of% by mass or more. Further, it is preferable that the green pigment does not substantially contain a green pigment (other green pigment) other than the color index pigment green 36 and the color index pigment green 7. The case where the other green pigment is substantially not contained means that the content of the other green pigment is 1% by mass or less, preferably 0.5% by mass or less, preferably 0.1% by mass. It is more preferable that it is as follows, and it is further preferable that it does not contain other green pigments.

The pigment dispersion liquid of the present invention may contain a yellow pigment (other yellow pigment) other than the color index pigment yellow 139 and the color index pigment yellow 150 as the yellow pigment. The yellow pigment used in the pigment dispersion of the present invention preferably contains 50% by mass or more, more preferably 80% by mass or more, and 90% by mass of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 in total. It is more preferably contained in an amount of% by mass or more. Further, it is preferable that the yellow pigment does not substantially contain a yellow pigment (other yellow pigment) other than the color index pigment yellow 139 and the color index pigment yellow 150. The case where the other yellow pigment is substantially not contained means that the content of the other yellow pigment is 1% by mass or less, preferably 0.5% by mass or less, preferably 0.1% by mass. It is more preferable that it is as follows, and it is further preferable that it does not contain other yellow pigments.

The pigment dispersion of the present invention preferably contains 50 to 100 parts by mass of a yellow pigment with respect to 100 parts by mass of a green pigment. The upper limit is preferably 95 parts by mass or less, more preferably 93 parts by mass or less, and further preferably 91 parts by mass or less. The lower limit is preferably 51 parts by mass or more, more preferably 52 parts by mass or more, and further preferably 53 parts by mass or more. According to this aspect, it is easy to form a cured film suitable for green pixels having spectral characteristics excellent in color separation from red and blue. Furthermore, it is easy to form a pattern having a higher rectangularity.

The pigment dispersion of the present invention preferably contains a total of 10 to 99% by mass of the green pigment and the yellow pigment with respect to the total solid content of the pigment dispersion. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more.

The pigment dispersion of the present invention has a total of 10 to 99 mass of color index pigment green 36, color index pigment green 7, color index pigment yellow 139 and color index pigment yellow 150 with respect to the total solid content of the pigment dispersion. % Is preferably contained. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. According to this aspect, it is easy to form a cured film suitable for green pixels having spectral characteristics excellent in color separation from red and blue. In particular, it is easy to form a cured film having high transmittance of light in the wavelength range of 500 to 550 nm and high shielding property against light in the wavelength range of 400 to 470 nm and light in the wavelength range of 600 to 700 nm. Furthermore, it is easy to form a pattern having a higher rectangularity.

In the pigment dispersion liquid of the present invention, examples of the solvent include the solvent described as a component contained in the above-mentioned coloring composition. The content of the solvent in the pigment dispersion is preferably such that the total solid content of the pigment dispersion is 5 to 95% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less.

The pigment dispersion liquid of the present invention preferably further contains a resin. Examples of the resin include the resins described as the components contained in the above-mentioned coloring composition. Among them, it is preferable to contain a resin containing a repeating unit having a nitrogen atom in the main chain. The content of the resin in the pigment dispersion is preferably 1 to 20% by mass with respect to the total solid content of the pigment dispersion. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more. The upper limit is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less.

The coloring composition of the present invention described above preferably contains the pigment dispersion liquid of the present invention.

<Manufacturing method of pigment dispersion liquid>
Next, the method for producing the pigment dispersion liquid of the present invention described above will be described.
The method for producing a pigment dispersion of the present invention includes a step of co-dispersing Color Index Pigment Green 36, Color Index Pigment Green 7, Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 in the presence of a solvent.
By co-dispersing these pigments in the presence of a solvent, the dispersibility of the pigments in the pigment dispersion liquid can be improved, and the aggregation of the pigments can be effectively suppressed. Further, since the aggregation of the pigments can be effectively suppressed, the effect that the dispersion stability is not easily lost due to the shock caused by drying or mixing with a solvent can be obtained.

In the method for producing a pigment dispersion liquid, examples of the mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing, and cavitation. 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. These details are the same as those described in the method for preparing the coloring composition. Further, in the method for producing a pigment dispersion liquid, it is preferable to filter with a filter for the purpose of removing foreign substances and reducing defects. The details of the filter filtration are the same as those described in the method for preparing the coloring composition.

<Hardened film>
The cured film of the present invention is a cured film obtained from the above-mentioned coloring composition of the present invention. The cured film of the present invention can be preferably used as a color filter. In particular, it can be preferably used as a green pixel of a color filter. The film thickness of the cured film can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.

The cured film of the present invention has a ratio (A _min / A ₄₅₀ ) of the minimum value A _min of the absorbance for light having a wavelength of 500 to 550 nm and the absorbance A ₄₅₀ for light having a wavelength of 450 nm (A min / A 450) of 0.02 to 0.09. It is preferably 0.03 to 0.08, more preferably 0.04 to 0.07. Further, the ratio (A _min / A ₆₀₀ ) of the minimum value A _min of the absorbance for light having a wavelength of 500 to 550 nm and the absorbance A ₆₀₀ for light having a wavelength of 600 nm is preferably 0.04 to 0.17, and is 0. It is more preferably .06 to 0.15, and even more preferably 0.08 to 0.13.

Further, the cured film of the present invention has a peak value of transmittance in the range of wavelength 500 to 550 nm in the transmission spectrum for light in the wavelength range of 400 to 700 nm, and has a peak value at which the transmittance is 50% of the peak value. The difference (λ1-λ2) between the wavelength λ1 on the long wave side of the wavelength and the wavelength λ2 on the short wave side of the peak value is preferably 90 to 112 nm, more preferably 93 to 109 nm, and 95 to. It is more preferably 107 nm.

Further, the cured film of the present invention preferably has a maximum transmittance of 80% or more, more preferably 83% or more, still more preferably 85% or more for light having a wavelength of 400 to 700 nm. .. Further, the average transmittance for light having a wavelength of 475 to 585 nm is preferably 60% or more, more preferably 65% or more, still more preferably 67% or more. Further, the cured film of the present invention preferably has a transmittance of 20% or less, more preferably 15% or less, and further preferably 13% or less with respect to light having a wavelength of 450 nm. Further, the cured film of the present invention preferably has a transmittance of 40% or less, more preferably 35% or less, and further preferably 33% or less with respect to light having a wavelength of 600 nm.

The cured film of the present invention preferably has a transmittance of 1 to 20%, more preferably 2 to 15%, and even more preferably 3 to 10% with respect to light having a wavelength of 365 nm.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned cured film of the present invention. A preferred embodiment of the color filter of the present invention includes an embodiment having a green pixel, a red pixel, and a blue pixel obtained from the coloring composition of the present invention.

In the color filter of the present invention, the film thickness of the cured film can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more. The color filter of the present invention can be used for a solid-state image pickup device such as a CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor), an image display device, or the like.

<Pattern formation method>
Next, a pattern forming method using the coloring composition of the present invention will be described. The pattern forming method includes a step of forming a colored composition layer on a support using the colored composition of the present invention, and a step of forming a pattern on the colored composition layer by a photolithography method. Is preferable.

The pattern formation by the photolithography method preferably includes a step of exposing the colored composition layer in a pattern and a step of developing and removing an unexposed portion to form a pattern. If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.

<< Step of forming the coloring composition layer >>
In the step of forming the coloring composition layer, the coloring composition is used to form the coloring composition layer on the support.

The support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate, a substrate for a solid image sensor provided with a solid image sensor (light receiving element) such as a CCD or CMOS, a silicon substrate, and the like. Further, if necessary, an undercoat layer may be provided on these base materials for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface.

As a method of applying the coloring composition on the support, various methods such as slit coating, inkjet method, rotation coating, cast coating, roll coating, screen printing method and the like can be used.

The colored composition layer formed on the support may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process. When prebaking is performed, the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. By performing the prebaking at 150 ° C. or lower, these characteristics can be more effectively maintained, for example, when the photoelectric conversion film of the image sensor is made of an organic material. The prebake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.

<< Exposure process >>
Next, the colored composition layer is exposed in a pattern (exposure step). For example, the colored composition layer can be exposed to a pattern by using an exposure device such as a stepper through a mask having a predetermined mask pattern. As a result, the exposed portion can be cured. As the radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). The irradiation amount (exposure amount) 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 appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment), or may be exposed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. The exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m ² to 100,000 W / m ² (for example, 5000 W / m ² , 15,000 W / m ² , or 35,000 W / m ² ). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined with each other. For example, the illuminance may be 10,000 W / m ² at an oxygen concentration of 10% by volume, an illuminance of 20,000 W / m ² at an oxygen concentration of 35% by volume, and the like.

<< Development process >>
Next, the unexposed portion is developed and removed to form a pattern. Development and removal of the unexposed portion can be performed using a developing solution. As a result, the colored composition layer of the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains on the support. As the developer, an organic alkaline developer that does not damage the underlying solid-state image sensor or circuit is desirable. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

As the developing solution, an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferably used. Examples of the alkaline agent include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxy. Do, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc. Examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms 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. Further, the developer may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. When a developer composed of such an alkaline aqueous solution is used, it is preferable to wash (rinse) it with pure water after development.

It is also possible to perform heat treatment (post-baking) after development and drying. Post-baking is a post-development heat treatment to complete the curing of the film. When post-baking is performed, the post-baking temperature is preferably, for example, 100 to 240 ° C. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. The Young's modulus of the film after post-baking is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa. Further, in the case where the support includes a material having low heat resistance (for example, an organic electroluminescence (organic EL) element or an image sensor having a photoelectric conversion film made of the organic material), the post-bake temperature is set. , 150 ° C. or lower is preferable, 120 ° C. or lower is more preferable, 100 ° C. or lower is further preferable, and 90 ° C. or lower is particularly preferable. The lower limit can be, for example, 50 ° C. or higher. Post-baking is performed continuously or in batch by using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so that the developed film (cured film) meets the above conditions. It can be carried out.

The cured film preferably has high flatness. Specifically, the surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. The lower limit is not specified, but it is preferably 0.1 nm or more, for example. The surface roughness can be measured by using, for example, AFM (Atomic Force Microscope) Definition 3100 manufactured by Veeco. Further, the contact angle of water on the cured film 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.).

It is desirable that the volume resistance value of the pattern (pixel) is high. Specifically, the volume resistance value of the pixel is preferably ^{109 Ω · cm or more, and more preferably 10 11 Ω} · cm or more. The upper limit is not specified, but it is preferably 10 ¹⁴ Ω · cm or less, for example. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).

<Solid image sensor>
The solid-state image sensor of the present invention has the color filter of the present invention described above. The configuration of the solid-state image pickup device of the present invention is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state image pickup device, and examples thereof include the following configurations.

On the substrate, a transfer electrode composed of a plurality of photodiodes constituting a light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and polysilicon, etc. It has a light-shielding film that opens only the light-receiving part of the photodiode on the photodiode and transfer electrode, and protects the device 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 light-receiving part of the photodiode. It has a film and has a color filter on the device protective film. Further, a configuration having a light-collecting means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (the side closer to the base material), a configuration having a light-collecting means on the color filter, and the like. May be. Further, the color filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned in a grid pattern by a partition wall. In this case, the partition wall preferably has a low refractive index for each colored pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757. The image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.

<Image display device>
The color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device. For details on the definition of image display devices and the details of each image display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)" )) ”, Etc. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by the following method.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 linked column developing solvent: tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 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

プロピレングリコールモノメチルエーテル（ＰＧＭＥ）・・・２．５７質量部
プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）・・・７１．７２質量部 <Preparation of pigment dispersion>
A mixed solution having the following composition was mixed and dispersed with a bead mill for 15 hours to prepare a pigment dispersion.
(Composition of mixed solution)
Color Index Pigment Green 36 ・ ・ ・ Mass part in the table below Color Index Pigment Green 7 ・ ・ ・ Mass part in the table below Color Index Pigment Yellow 150 ・ ・ ・ Mass part Color Index Pigment Yellow 139 ・ ・ ・ in the table below In the table below, parts by mass Resin (Acrycure RD-F8, manufactured by Nippon Catalyst Co., Ltd.) ... 3.21 parts by mass Resin (resin with the following structure, weight average molecular weight 18,000, the values added to the main chain are molars. Ratio) ・ ・ ・ 6.43 parts by mass

Propylene glycol monomethyl ether (PGME) ・ ・ ・ 2.57 parts by mass Propylene glycol monomethyl ether acetate (PGMEA) ・ ・ ・ 71.72 parts by mass

In the above table, PG36 is Color Index Pigment Green 36, PG7 is Color Index Pigment Green 7, PY150 is Color Index Pigment Yellow 150, and PY139 is Color Index Pigment Yellow 139.

光重合開始剤（ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＢＡＳＦ製）・・・１．７８質量部
紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）・・・０．７９質量部
ＰＧＭＥＡ・・・３７．２１質量部 <Preparation of coloring composition>
The following raw materials were mixed to prepare a coloring composition.
(Composition of coloring composition)
Pigment dispersion: 52.17 parts by mass, polymerizable compound (NK ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.): 2.67 parts by mass, polymerizable compound (KAYARAD DPHA, Nippon Kayaku) Co., Ltd.) ・ ・ ・ 0.77 parts by mass Resin (Acrycure RD-F8, manufactured by Nippon Catalyst Co., Ltd.) ・ ・ ・ 0.44 parts by mass Surface active agent (compound with the following structure, weight average molecular weight 14000, repeated) The% indicating the ratio of the unit is mass%. PGMEA 0.2 mass% solution) ... 4.17 parts by mass

Photopolymerization initiator (IRGACURE-OXE02, manufactured by BASF) ... 1.78 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ... 0.79 parts by mass PGMEA ... 37.21 Mass part

<Preparation of cured film>
The coloring composition was applied onto a glass substrate by spin coating so as to form a coating film having a film thickness of 0.89 μm, and prebaked at 100 ° C. for 180 seconds using a hot plate. Next, this was exposed with an i-line at an exposure amount of 1000 mj / cm 2, and then heated at 220 ° C. for 5 minutes to prepare a cured film having a thickness of 0.8 μm.

<Spectroscopic evaluation>
With respect to the obtained cured film, the light transmittance (transmittance) in the range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. These cured films had a transmittance peak in the wavelength range of 500 to 550 nm. The spectral characteristics of each cured film are shown in the table below. In the table below, λ1 and λ2 are wavelengths at which the transmittance is 50% of the peak value, respectively, λ1 is the wavelength on the long wave side of the wavelength of the peak value, and λ2 is the wavelength of the peak value. It is the wavelength on the short wave side of the wavelength.

(Evaluation of rectangularness)
<Making a silicon wafer substrate with an undercoat layer>
A silicon wafer having a diameter of 8 inches (1 inch = 25.4 mm) was heat-treated in an oven at 200 ° C. for 30 minutes. Next, a resist solution for undercoating (CT-4000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied onto this silicon wafer so that the dry film thickness was 0.1 μm, and further in an oven at 220 ° C. 1 The undercoat layer was formed by heating and drying for an hour to obtain a silicon wafer substrate with an undercoat layer.
Each coloring composition was applied onto the undercoat layer of a silicon wafer substrate with an undercoat layer so as to form a coating film having a film thickness of 0.89 μm. Then, a heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100 ° C. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at a wavelength of 365 nm and an exposure amount of 500 mJ / cm ² through a mask having a pattern. As the mask, a mask having a Bayer pattern of 1.4 μm × 1.4 μm was used.
After that, the substrate on which the irradiated coating film was formed was placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and the alkaline developer CD-2060 (Fuji) was placed. A pattern was formed by paddle-development for 60 seconds at room temperature using Film Electronics Materials Co., Ltd.
Next, the substrate on which the pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and while the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is ejected from above the center of rotation in a shower shape. Was supplied to the silicon and rinsed (23 seconds x 2 times). Then, after spin drying, post-baking was performed on a hot plate at 200 ° C. for 300 seconds to obtain a pattern.

The obtained patterned silicon wafer was cut, the cross section of the pattern was magnified 20,000 times using a scanning electron microscope (SEM), and the rectangularity was evaluated according to the following criteria.
A: The width of the lower part in contact with the undercoat layer is in the range of 90% or more and 130% or less with respect to the width of the upper part of the pattern.
B: The width of the lower part in contact with the undercoat layer is 80% or more and less than 90%, or more than 130% and less than 160% with respect to the width of the upper part of the pattern.
C: The width of the lower part in contact with the undercoat layer is less than 80% or more than 160% with respect to the width of the upper part of the pattern.

As shown in the above table, the cured film of the example had a high transmittance of light having a wavelength of 530 nm and was excellent in sensitivity as a green pixel. In addition, the transmittance at a wavelength of 450 nm and a wavelength of 600 nm was low, and the color separation from blue and red was superior to that of Comparative Example 1. Further, when a pattern was formed using each coloring composition, it was possible to form a pattern having better rectangularity than the case where the coloring composition of Comparative Example was used by using the coloring composition of Examples. ..

Claims (30)

Contains green pigments, yellow pigments, photopolymerization initiators, polymerizable compounds and solvents,
The green pigment comprises at least Color Index Pigment Green 36 and Color Index Pigment Green 7.
The yellow pigment comprises at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.
The mass ratio of the color index pigment green 36 and the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50.
The mass ratio of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 is Color Index Pigment Yellow 139: Color Index Pigment Yellow 150 = 1: 99 to 10:90.
The green pigment contains 90% by mass or more of Color Index Pigment Green 36 and Color Index Pigment Green 7 in total.
A coloring composition which is a coloring composition for forming green pixels in a color filter . Color Index Pigment Green 36 and Color Index Pigment Green 7 total 100 parts by mass, Color Index Pigment Yellow 139 by 0.05 to 20 parts by mass, and Color Index Pigment Yellow 150 by 49.95 to 99.9. The coloring composition according to claim 1, which comprises a part by mass. Contains green pigments, yellow pigments, photopolymerization initiators, polymerizable compounds and solvents,
The green pigment comprises at least Color Index Pigment Green 36 and Color Index Pigment Green 7.
The yellow pigment comprises at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.
The mass ratio of the color index pigment green 36 and the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50.
For a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7, 1.0 to 5 parts by mass of Color Index Pigment Yellow 139 is included.
The green pigment is a coloring composition containing 90% by mass or more of Color Index Pigment Green 36 and Color Index Pigment Green 7 in total. The coloring according to claim 3, wherein the mass ratio of the color index pigment yellow 139 and the color index pigment yellow 150 is color index pigment yellow 139: color index pigment yellow 150 = 0.1: 99.9 to 20:80. Composition. The coloring composition according to any one of claims 1 to 4, wherein the green pigment contains 1% by mass or less of a green pigment other than the color index pigment green 36 and the color index pigment green 7. 13. Coloring composition. The coloring composition according to any one of claims 1 to 6, wherein the yellow pigment is contained in an amount of 50 to 100 parts by mass with respect to 100 parts by mass of the green pigment. The coloring composition according to any one of claims 1 to 7, which contains 5.7 to 8.2 parts by mass of Color Index Pigment Yellow 139 with respect to 100 parts by mass of Color Index Pigment Green 36. Any of claims 1 to 8, wherein the color index pigment yellow 139 and the color index pigment yellow 150 are included in a total of 50 to 100 parts by mass with respect to a total of 100 parts by mass of the color index pigment green 36 and the color index pigment green 7. The coloring composition according to item 1. Claim 1 to 100 parts by mass of Color Index Pigment Green 36, 0.1 to 80 parts by mass of Color Index Pigment Yellow 139, and 99.9 to 399.6 parts by mass of Color Index Pigment Yellow 150. 9. The coloring composition according to any one of 9. The coloring composition according to any one of claims 1 to 10, which contains 99.9 to 200 parts by mass of Color Index Pigment Yellow 150 with respect to 100 parts by mass of Color Index Pigment Green 36. The coloring composition according to any one of claims 1 to 11, which contains 132 to 158 parts by mass of Color Index Pigment Yellow 150 with respect to 100 parts by mass of Color Index Pigment Green 36. The coloring composition according to any one of claims 1 to 12, wherein the polymerizable compound contains a polymerizable compound having an alkyleneoxy group. The coloring composition according to any one of claims 1 to 13, further comprising a resin. The coloring composition according to claim 14, wherein the resin contains a resin containing a repeating unit having a nitrogen atom in the main chain. The coloring composition according to claim 14, wherein the resin contains an alkali-soluble resin having a polymerizable group. The coloring composition according to any one of claims 1 to 16, further comprising an ultraviolet absorber. Minimum value of absorbance for light with a wavelength of 500 to 550 nm A _min And the absorbance A for light with a wavelength of 450 nm ₄₅₀ Ratio with (A _min / A ₄₅₀ ) Is 0.02 to 0.09, and the minimum value A of the absorbance for light having a wavelength of 500 to 550 nm. _min And the absorbance A for light with a wavelength of 600 nm ₆₀₀ Ratio with (A _min / A ₆₀₀ ) Is 0.04 to 0.17, according to any one of claims 1 to 17. Contains green pigments, yellow pigments and solvents,
The green pigment comprises at least Color Index Pigment Green 36 and Color Index Pigment Green 7.
The yellow pigment comprises at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.
The mass ratio of the color index pigment green 36 and the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50.
The mass ratio of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 is Color Index Pigment Yellow 139: Color Index Pigment Yellow 150 = 1: 99 to 10:90.
The green pigment contains 90% by mass or more of Color Index Pigment Green 36 and Color Index Pigment Green 7 in total, and is a pigment dispersion which is a raw material of the coloring composition according to any one of claims 1 to 18. .. Contains green pigments, yellow pigments and solvents,
The green pigment comprises at least Color Index Pigment Green 36 and Color Index Pigment Green 7.
The yellow pigment comprises at least Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150.
The mass ratio of the color index pigment green 36 and the color index pigment green 7 is color index pigment green 36: color index pigment green 7 = 25: 75 to 50:50.
For a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7, 1.0 to 5 parts by mass of Color Index Pigment Yellow 139 is included.
The green pigment contains 90% by mass or more of Color Index Pigment Green 36 and Color Index Pigment Green 7 in total, and is a raw material for the coloring composition according to any one of claims 1 to 18, pigment dispersion. liquid. The pigment dispersion according to claim 19 or 20, wherein the green pigment contains 1% by mass or less of a green pigment other than the color index pigment green 36 and the color index pigment green 7. Any of claims 19 to 21, which comprises 50 to 100 parts by mass of Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 with respect to a total of 100 parts by mass of Color Index Pigment Green 36 and Color Index Pigment Green 7. The pigment dispersion liquid according to item 1. The pigment dispersion according to any one of claims 19 to 22, which contains 5.7 to 8.2 parts by mass of Color Index Pigment Yellow 139 with respect to 100 parts by mass of Color Index Pigment Green 36. The pigment dispersion according to any one of claims 19 to 23, which comprises 99.9 to 200 parts by mass of Color Index Pigment Yellow 150 with respect to 100 parts by mass of Color Index Pigment Green 36. The pigment dispersion according to any one of claims 19 to 24, which comprises 132 to 158 parts by mass of Color Index Pigment Yellow 150 with respect to 100 parts by mass of Color Index Pigment Green 36. The method for producing a pigment dispersion according to any one of claims 19 to 25.
A method for producing a pigment dispersion, which comprises a step of co-dispersing Color Index Pigment Green 36, Color Index Pigment Green 7, Color Index Pigment Yellow 139 and Color Index Pigment Yellow 150 in the presence of a solvent. A cured film obtained from the coloring composition according to any one of claims 1 to 18. A color filter including the cured film according to claim 27. The solid-state image sensor having the color filter according to claim 28. An image display device having the color filter according to claim 28.