JP7090628B2 - Coloring composition, cured film, pattern forming method, color filter, solid-state image sensor and image display device - Google Patents

Description

The present invention relates to a coloring composition, a cured film, a pattern forming method, 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. A color filter usually includes pixels (coloring patterns) of the three primary colors of red, green, and blue, and plays a role of decomposing transmitted light into the three primary colors.

Diketopyrrolopyrrole pigments such as Color Index Pigment Red 254 are used in the coloring composition for forming red pixels. For example, Patent Documents 1 to 3 describe manufacturing a color filter using a coloring composition containing Color Index Pigment Red 254.

Japanese Unexamined Patent Publication No. 2009-96977 Japanese Unexamined Patent Publication No. 2011-153280 Japanese Unexamined Patent Publication No. 2010-217872

However, the coloring composition containing the diketopyrrolopyrrole pigment cannot be said to have sufficient coatability, and tends to cause uneven thickness.

Therefore, an object of the present invention is to provide a coloring composition having good coatability and capable of producing a film having suppressed thickness unevenness. Another object of the present invention is to provide a cured film, a pattern forming method, a color filter, a solid-state image pickup device, and an image display device.

式中、Ｒ^１およびＲ^２は、それぞれ独立して、ハロゲン原子、アルキル基、シアノ基、ニトロ基、－ＣＯＯＲ^Ｄ１、－ＳＯ_２Ｒ^Ｄ１、－ＯＲ^Ｄ１、－ＳＲ^Ｄ１または－ＮＲ^Ｄ１Ｒ^Ｄ２を表し、
Ｒ^Ｄ１およびＲ^Ｄ２は、それぞれ独立して、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、
ｍ１およびｍ２はそれぞれ独立して０～５の整数を表し、
ｍ１が２以上の場合、ｍ１個のＲ^１はそれぞれ同一であってもよく、異なっていてもよく、
ｍ２が２以上の場合、ｍ２個のＲ^２はそれぞれ同一であってもよく、異なっていてもよい。
＜２＞ 式（ＤＰＰ）で表される顔料が、カラーインデックスピグメントレッド２５４、カラーインデックスピグメントレッド２５５、カラーインデックスピグメントレッド２７２、カラーインデックスピグメントオレンジ７１、および、カラーインデックスピグメントオレンジ７３から選ばれる少なくとも１種である、＜１＞に記載の着色組成物。
＜３＞ グラフト鎖は、式（Ｇ－１）、式（Ｇ－２）または式（Ｇ－３）で表される構造である、＜１＞または＜２＞に記載の着色組成物；

Ｒ^Ｇ１は、アルキレン基を表し、Ｗ^１００は水素原子または置換基を表す。ｎ１～ｎ３は、それぞれ独立して３以上の整数を表す。
＜４＞ グラフト鎖は、ε－カプロラクトンおよびδ－バレロラクトンから選ばれる化合物由来のポリエステル構造を含む、＜１＞～＜３＞のいずれかに記載の着色組成物。
＜５＞ 繰り返し単位Ａの重量平均分子量が１０００以上である、＜１＞～＜４＞のいずれかに記載の着色組成物。
＜６＞ 重合性化合物は、酸基を有する重合性化合物を含む、＜１＞～＜５＞のいずれかに記載の着色組成物。
＜７＞ 重合性化合物の含有量が、グラフト樹脂の１００質量部に対して１００質量部以下である、＜１＞～＜６＞のいずれかに記載の着色組成物。
＜８＞ グラフト樹脂の含有量が、式（ＤＰＰ）で表される顔料の１００質量部に対して３０～９０質量部である、＜１＞～＜７＞のいずれかに記載の着色組成物。
＜９＞ 回転粘度計を使用し、せん断速度１０ｓ^－１で測ったときの２３℃での粘度μ_１に対する、せん断速度１０００ｓ^－１で測ったときの２３℃での粘度μ_２の比であるμ_２／μ_１が０．７５以上１．２５以下である、＜１＞～＜８＞のいずれかに記載の着色組成物。
＜１０＞ ＜１＞～＜９＞のいずれかに記載の着色組成物を硬化して得られる硬化膜。
＜１１＞ ＜１＞～＜９＞のいずれかに記載の着色組成物を用いて支持体上に着色組成物層を形成する工程と、
着色組成物層をパターン状に露光する工程と、
着色組成物層の未露光部を現像除去する工程と、
を含むパターン形成方法。
＜１２＞ ＜１０＞に記載の硬化膜を含むカラーフィルタ。
＜１３＞ ＜１０＞に記載の硬化膜を有する固体撮像素子。
＜１４＞ ＜１０＞に記載の硬化膜を有する画像表示装置。As a result of diligent studies, the present inventor has found that the coloring composition described later can produce a film having good coatability and suppressed thickness unevenness, and has completed the present invention. That is, the present invention is as follows.
<1> A coloring composition containing a pigment represented by the formula (DPP), a resin, a photopolymerization initiator, and a polymerizable compound.
The resin contains a graft resin having a poly (meth) acrylate structure as a main chain and a polyester structure graft chain on the side chain and containing 20 mol% or more of the repeating unit A.
A coloring composition in which 60% by mass or more of the resin contained in the coloring composition is a graft resin;
Equation (DPP)

In the formula, R ¹ and R ² are independently halogen atoms, alkyl groups, cyano groups, nitro groups, -COOR ^D1 , -SO ₂ R ^D1 , -OR ^D1 , -SR ^D1 or -NR ^D1 R ^D2 , respectively. Represents
R ^D1 and R ^D2 independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, respectively.
m1 and m2 independently represent integers from 0 to 5, respectively.
When m1 is 2 or more, m1 ^R1s may be the same or different.
When m2 is 2 or more, the ^m2 R2s may be the same or different.
<2> The pigment represented by the formula (DPP) is at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 255, Color Index Pigment Red 272, Color Index Pigment Orange 71, and Color Index Pigment Orange 73. The coloring composition according to <1>, which is a seed.
<3> The coloring composition according to <1> or <2>, wherein the graft chain has a structure represented by the formula (G-1), the formula (G-2) or the formula (G-3);

^RG1 represents an alkylene group and ^W100 represents a hydrogen atom or a substituent. Each of n1 to n3 independently represents an integer of 3 or more.
<4> The coloring composition according to any one of <1> to <3>, wherein the graft chain contains a polyester structure derived from a compound selected from ε-caprolactone and δ-valerolactone.
<5> The coloring composition according to any one of <1> to <4>, wherein the repeating unit A has a weight average molecular weight of 1000 or more.
<6> The coloring composition according to any one of <1> to <5>, wherein the polymerizable compound contains a polymerizable compound having an acid group.
<7> The coloring composition according to any one of <1> to <6>, wherein the content of the polymerizable compound is 100 parts by mass or less with respect to 100 parts by mass of the graft resin.
<8> The coloring composition according to any one of <1> to <7>, wherein the content of the graft resin is 30 to 90 parts by mass with respect to 100 parts by mass of the pigment represented by the formula (DPP). ..
<9> The ratio of the viscosity μ ₁ at 23 ° C. measured at a shear rate of 10s ^-1 to the viscosity μ ₂ at 23 ° C. measured at a shear rate 1000s ^-1 using a rotational viscometer. The coloring composition according to any one of <1> to <8>, wherein μ ₂ / μ ₁ is 0.75 or more and 1.25 or less.
<10> A cured film obtained by curing the coloring composition according to any one of <1> to <9>.
<11> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <9>, and
The process of exposing the coloring composition layer in a pattern and
The process of developing and removing the unexposed portion of the coloring composition layer,
Pattern forming method including.
<12> A color filter containing the cured film according to <10>.
<13> The solid-state image sensor having the cured film according to <10>.
<14> An image display device having the cured film according to <10>.

According to the present invention, it is possible to provide a coloring composition having good coatability and capable of producing a film having suppressed thickness unevenness. Further, it is possible to provide a cured film, a pattern forming method, 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 those having no substituent as well as those having a 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).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, examples of the light used for exposure generally include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, 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.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate". ) Allyl "represents both allyl and / or methacrylic, and" (meth) acryloyl "represents both / or either acryloyl and methacrylic acid.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
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).
As used herein, the term pigment means an insoluble dye compound that is difficult to dissolve in a solvent. The pigment used in the present invention preferably has, for example, a dissolution amount in 100 g of propylene glycol monomethyl ether acetate at 25 ° C. and a dissolution amount in 100 g of water at 25 ° C. of 0.1 g or less. It is more preferably 05 g or less, and further preferably 0.01 g or less.

The coloring composition of the present invention is a coloring composition containing a pigment represented by the formula (DPP) described later, a resin, a photopolymerization initiator, and a polymerizable compound.
The above resin contains a graft resin containing 20 mol% or more of a repeating unit A having a poly (meth) acrylate structure as a main chain and a polyester structure graft chain as a side chain.
It is characterized in that 60% by mass or more of the resin contained in the coloring composition is the above-mentioned graft resin.

According to the study of the present inventor, the diketopyrrolopyrrole pigment tends to have a relatively high interaction between the pigments, and the coloring composition containing the diketopyrrolopyrrole pigment has a viscosity as the shear rate increases. It was found that the decrease was large and the amount of change in viscosity with respect to the shear rate tended to be large. Since the coloring composition containing the diketopyrrolopyrrole pigment has such a viscosity characteristic, it is presumed that thickness unevenness is likely to occur. For example, when a coloring composition containing a diketopyrrolopyrrole pigment is applied by spin coating, the centrifugal force becomes stronger as the distance from the center of rotation increases, so that the film thickness near the center of rotation becomes thicker than the film thickness on the outer periphery. It is presumed that the thickness is likely to be uneven, and as a result, the thickness unevenness is likely to occur.
According to the coloring composition of the present invention, 60 of a pigment represented by the formula (DPP) described later (hereinafter, also referred to as a pigment (DPP)) and a graft resin containing 20 mol% or more of the above-mentioned specific repeating unit A. Since it contains a resin containing mass% or more, the interaction between the pigments (DPP) in the coloring composition is small, and the dispersibility of the pigment (DPP) is good. Therefore, the amount of change in viscosity with respect to the shear rate is small. As a result, it is presumed that a film having good coatability and suppressed thickness unevenness could be produced. Therefore, the coloring composition of the present invention can produce a film having good coatability and suppressed thickness unevenness.

The coloring composition uses at least one selected from Color Index Pigment Red 254, Color Index Pigment Red 255, Color Index Pigment Red 272, Color Index Pigment Orange 71, and Color Index Pigment Orange 73 as the pigment (DPP). In this case, the effect of improving the thickness unevenness is remarkably exhibited, and when the color index pigment red 254 is used as the pigment (DPP), the effect of improving the thickness unevenness is remarkably exhibited.

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

式中、Ｒ^１およびＲ^２は、それぞれ独立して、ハロゲン原子、アルキル基、シアノ基、ニトロ基、－ＣＯＯＲ^Ｄ１、－ＳＯ_２Ｒ^Ｄ１、－ＯＲ^Ｄ１、－ＳＲ^Ｄ１または－ＮＲ^Ｄ１Ｒ^Ｄ２を表し、Ｒ^Ｄ１およびＲ^Ｄ２は、それぞれ独立して、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、ｍ１およびｍ２はそれぞれ独立して０～５の整数を表し、ｍ１が２以上の場合、ｍ１個のＲ^１はそれぞれ同一であってもよく、異なっていてもよく、ｍ２が２以上の場合、ｍ２個のＲ^２はそれぞれ同一であってもよく、異なっていてもよい。<< Pigment represented by formula (DPP) >>
The coloring composition of the present invention contains a pigment represented by the formula (DPP). This pigment is a pigment having a diketopyrrolopyrrole skeleton. Hereinafter, the pigment represented by the formula (DPP) is also referred to as a pigment (DPP).
Equation (DPP)

In the formula, R ¹ and R ² are independently each of a halogen atom, an alkyl group, a cyano group, a nitro group, -COOR ^D1 , -SO ₂ R ^D1 , -OR ^D1 , -SR ^D1 or -NR ^D1 R ^D2 . R ^D1 and R ^D2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, m1 and m2 each independently represent an integer of 0 to 5, and m1 is 2 or more. In the case of, the m1 ^R1s may be the same or different, and when m2 is 2 or more, the ^m2 R2s may be the same or different.

Examples of the halogen atom represented by R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of carbon atoms of the alkyl group represented by R ¹ , R ² , R ^{D 1} and R ^{D 2} is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched or cyclic, preferably linear or branched. The alkyl group may have a substituent. Examples of the substituent include the groups listed in Substituent T described later.

The aryl group represented by ^RD1 and ^RD2 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. The aryl group may have a substituent. Examples of the substituent include the groups listed in Substituent T described later.
The heteroaryl group represented by ^RD1 and ^RD2 may be a monocyclic ring or a fused ring. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The heteroaryl group may have a substituent. Examples of the substituent include the groups listed in Substituent T described later.

R ¹ and R ² are preferably independent halogen atoms, alkyl groups or cyano groups, more preferably halogen atoms or alkyl groups, and even more preferably halogen atoms.

m1 and m2 each independently represent an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1.

Examples of the substituent T include the following groups. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group). Aryl groups with 6 to 30 carbon atoms), amino groups (preferably amino groups with 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups with 1 to 30 carbon atoms), aryloxy groups (preferably 6 to 30 carbon atoms). 30 aryloxy groups), heteroaryloxy groups, acyl groups (preferably acyl groups having 1 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl groups). Is an aryloxycarbonyl group having 7 to 30 carbon atoms), a heteroaryloxycarbonyl group, an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), and an alkoxy. A carbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably an alkoxycarbonylamino group having 0 to 30 carbon atoms). Sulfamoyl group), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), hetero Arylthio groups (preferably 1 to 30 carbon atoms), alkylsulfonyl groups (preferably 1 to 30 carbon atoms), arylsulfonyl groups (preferably 6 to 30 carbon atoms), heteroarylsulfonyl groups (preferably 1 to 30 carbon atoms). 30), alkylsulfinyl group (preferably 1 to 30 carbon atoms), arylsulfinyl group (preferably 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1 to 30 carbon atoms), ureido group (preferably carbon number 1 to 30). 1-30), hydroxy group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imide acid group, mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group , Hydradino group, imino group, heteroaryl group (preferably 1 to 30 carbon atoms). These groups may have additional substituents if they are further substitutable groups. Examples of the substituent include the group described in the above-mentioned Substituent T.

Specific examples of the pigment (DPP) include compounds having the following structures. In the table below, when the indication of the substituent is "-", it indicates that it is a hydrogen atom. For example, DPP-1 indicates that Z ¹ , Z ³ to Z ¹⁰ are hydrogen atoms and Z ² is -OCH ₃ . Further, Me represents a methyl group and Ph represents a phenyl group.

Among the compounds having the above structure, compound PR254 is Color Index (CI) Pigment Red 254, and compound PR255 is C.I. I. Pigment Red 255, compound PR272 is C.I. I. Pigment Red 272, and compound PO71 is C.I. I. Pigment Orange 71, and compound PO73 is C.I. I. Pigment Orange 73.

In the present invention, as the pigment (DPP), Color Index (CI) Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 272, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73 is preferable, and C.I. I. Pigment Red 254 is more preferred.

The content of the pigment (DPP) is preferably 30% by mass or more, more preferably 33% by mass or more, and further preferably 35% by mass or more in the total solid content of the coloring composition. The upper limit can be 55% by mass or less.
The proportion of the pigment (DPP) in the total mass of the colorant contained in the coloring composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 65% by mass or more. Is even more preferable. The upper limit can be 100% by mass or less.

<< Other colorants >>
The coloring composition of the present invention can contain a coloring agent other than the pigment (DPP) (hereinafter, also referred to as another coloring agent). The other colorant may be a pigment or a dye. Pigments and dyes may be used in combination. The colorant used in the present invention preferably contains a pigment. The content of the pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and further preferably 90% by mass or more. Is particularly preferred. Further, the colorant may be only a pigment.

Examples of the pigment include inorganic pigments and organic pigments, and organic pigments are preferable. Examples of the organic pigment include those shown below.

C. I. Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1,36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97, 98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179, 180,181,182,185,187,188,193,194,199,213,214 etc. (above, yellow pigment),
C. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64 etc. Color pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48: 2,48:3,48:4 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,264,269,270,279 etc. (above, red pigment),
C. I. Pigment Green 7,10,36,37,58,59, etc. (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42, etc. (above, purple pigment),
C. I. 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 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 is used. You can also do it. Specific examples include the compounds described in International Publication WO2015 / 118720.
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 JP2014-26228, and the like can also be used.

In addition, a dye multimer can be used as another colorant. The dye multimer is preferably a dye used by dissolving it in a solvent, but the dye multimer may form particles, and when the dye multimer is a particle, it is usually dispersed in a solvent. Used. The dye multimer in the particle state can be obtained, for example, by emulsion polymerization, and the compounds and production methods described in JP-A-2015-214682 are specific examples. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may have the same dye structure or may have different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. 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.

The other colorants are preferably yellow colorants, more preferably yellow pigments, and C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150 and C.I. I. More preferably, it is one or more selected from Pigment Yellow 185, and C.I. I. Pigment Yellow 139 and C.I. I. More preferably, it is one or more selected from Pigment Yellow 185, and C.I. I. Pigment Yellow 139 is particularly preferred. According to this aspect, more excellent coatability can be easily obtained. Further, preferable spectral characteristics in terms of color reproducibility can be obtained.

When the coloring composition of the present invention contains another colorant (that is, a colorant other than the pigment (DPP)), the content of the other colorant is 10 to 100 parts by mass with respect to 100 parts by mass of the pigment (DPP). It is preferably 100 parts by mass. The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less.
The content of the yellow colorant is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the pigment (DPP). The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less.
Further, the total content of the pigment (DPP) and other colorants is preferably 30 to 70% by mass in the total solid content of the coloring composition. The lower limit is preferably 40% by mass or more, and more preferably 45% by mass or more. The upper limit is preferably 65% by mass or less, and more preferably 60% by mass or less.
The total content of the pigment (DPP) and the yellow colorant is preferably 30 to 70% by mass in the total solid content of the coloring composition. The lower limit is preferably 40% by mass or more, and more preferably 45% by mass or more. The upper limit is preferably 65% by mass or less, and more preferably 60% by mass or less.

<< Resin >>
The coloring composition of the present invention contains a resin. In the present invention, the resin is an organic compound other than a colorant and has a molecular weight of 2,000 or more. The resin is blended, for example, for the purpose of dispersing particles such as pigments in a composition or for a binder. A resin mainly used for dispersing particles such as pigments 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.

(Graft resin A)
The coloring composition of the present invention is a graft resin containing 20 mol% or more of a repeating unit A having a poly (meth) acrylate structure as a main chain and a polyester structure graft chain in a side chain as a resin (hereinafter, also referred to as graft resin A). Includes). This graft resin A is preferably used as a dispersant for a pigment (DPP). In addition, in this specification, a graft resin means a resin which has a graft chain. Further, the graft chain indicates from the root of the main chain of the polymer to the end of the group branched from the main chain.

The repeating unit A in the graft resin A is a repeating unit having a poly (meth) acrylate structure as a main chain and a polyester structure graft chain as a side chain.

In the present invention, the graft chain in the graft resin A means a polymer chain that branches and extends from the main chain of the 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 (DPP) can be enhanced. The graft chain preferably has 40 to 10000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and 60 to 60 to 2000 atoms excluding hydrogen atoms. It is more preferably 500.

The number of repetitions of the polyester in the graft chain is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more, from the viewpoint of dispersibility of the pigment (DPP).

Ｒ^Ｇ１は、アルキレン基を表し、Ｗ^１００は水素原子または置換基を表す。ｎ１～ｎ３は、それぞれ独立して３以上の整数を表す。Examples of the graft chain include structures represented by the formula (G-1), the formula (G-2) or the formula (G-3).

^RG1 represents an alkylene group and ^W100 represents a hydrogen atom or a substituent. Each of n1 to n3 independently represents an integer of 3 or more.

The carbon number of the alkylene group represented by ^RG1 is preferably 1 to 20, more preferably 2 to 16, and even more preferably 3 to 12. The alkylene group is preferably linear or branched, more preferably linear.

Each of n1 to n3 independently represents an integer of 3 or more, more preferably 4 or more, and further preferably 5 or more. The upper limit is, for example, preferably 100 or less, more preferably 80 or less, and even more preferably 60 or less.

W ¹⁰⁰ represents 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 the pigment (DPP). The alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.

From the viewpoint of improving the dispersibility of the pigment (DPP), the graft chain of the graft resin A preferably contains a polyester structure derived from a compound selected from ε-caprolactone and δ-valerolactone. Examples of the polyester structure derived from ε-caprolactone include the following structures represented by ε-CL. Examples of the polyester structure derived from δ-valerolactone include the following structures represented by δ-VL.

The repeating unit A in the graft resin A is preferably a repeating unit represented by the following formula (GA).
Equation (GA)

In the formula, ^RA1 represents a hydrogen atom or an alkyl group, ^LA1 represents a single bond or a divalent linking group, and ^WA1 represents a graft chain having a polyester structure.

The number of carbon atoms of the alkyl group represented by ^RA1 is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. ^RA1 is preferably a hydrogen atom or a methyl group.

Examples of the divalent linking group represented by ^LA1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, and -SO-. Examples thereof include -SO _2- , -CO-, -O-, -COO-, OCO-, -S-, and a group consisting of a combination of two or more of these. The alkylene group may be linear, branched, or cyclic, and is preferably linear or branched.

^WA1 represents a graft chain having a polyester structure. Examples of the graft chain having a polyester structure include the above-mentioned graft chain, and a graft chain having a structure represented by the above formula (G-1), formula (G-2) or formula (G-3) is preferable.

In the graft resin A, the weight average molecular weight (Mw) of the repeating unit A is preferably 300 or more, more preferably 300 to 10000, and even more preferably 1000 to 7500. In the present invention, the weight average molecular weight of the repeating unit A is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit. For example, the repeating unit A can be formed by polymerizing a macromonomer. Here, the macromonomer means a polymer compound having a polymerizable group introduced at the end of the polymer. When the repeating unit A is formed by using the macromonomer, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the repeating unit A.

The graft resin A contains 20 mol% or more of the repeating unit A in all the repeating units of the graft resin A, preferably 21 mol% or more, more preferably 22 mol% or more, and 23 mol% or more. Is even more preferable. The upper limit can be 100 mol%, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less. can.

The graft resin A used in the present invention may further contain a repeating unit other than the repeating unit A. Examples of the other repeating unit include a repeating unit having an acid group, a repeating unit having a polymerizable group, and the like. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group. Examples of the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

By further containing the repeating unit having an acid group in the graft resin A, the effect of imparting alkali developability and improving the resolution can be expected. Further, when the graft resin A further contains a repeating unit having a polymerizable group, it is easy to obtain a cured film having excellent various physical properties such as heat resistance.

When the graft resin A contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 50 to 80 mol% in all the repeating units of the graft resin A. The lower limit is preferably 55 mol% or more, more preferably 60 mol% or more. The upper limit is preferably 78 mol% or less, more preferably 77 mol% or less.
When the graft resin A contains a repeating unit having a polymerizable group, the content of the repeating unit having a polymerizable group is preferably 10 to 40 mol% in all the repeating units of the graft resin A. The lower limit is preferably 15 mol% or more, more preferably 20 mol% or more. The upper limit is preferably 35 mol% or less, more preferably 30 mol% or less.

Specific examples of the graft resin A include a resin having the following structure. Further, regarding the graft resin A, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.

(Other resins)
The coloring composition of the present invention can further contain a resin other than the above-mentioned graft resin A (hereinafter, also referred to as another resin). Examples of other resins include resins having no graft chain (linear organic polymer polymer). Examples of other resins include alkali-soluble resins and the like.

The alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali dissolution. Examples of the group that promotes alkali dissolution (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy 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 having a carboxyl group in the side chain. For example, polymers having repeating units derived from monomers 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 hydroxy 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 the 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-substituted maleimide monomers 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. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in the side chain or the like is useful. 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 Fujifilm 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.

Specific examples of the ether dimer include the compounds described in paragraph No. 0317 of JP2013-29760A, the contents of which are incorporated in the present specification. The ether dimer may be only one kind or two or more kinds.

Examples of the polymer obtained by polymerizing a monomer component containing an ether dimer include a polymer having the following structure.

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 having 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, in the copolymer (B) described in paragraphs 0029 to 0063 of JP2012-32767A and the alkali-soluble resin used in Examples, paragraph numbers 0088 to 0098 of JP2012-208474A. The binder resin described and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A, and the binder resin used in the examples, JP2013-024934. Binder resin described in paragraph numbers 0132 to 0143 of Japanese Patent Laid-Open No. 0132 to 0143 and the binder resin used in Examples, paragraph numbers 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and the binder resin used in Examples of Japanese Patent Application Laid-Open No. 2012 It is also possible to use the binder resin described in paragraphs 0030 to 0072 of Japanese Patent Publication No. 323770. These contents 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.

In the coloring composition of the present invention, the content of the resin is preferably 1 to 80% by mass in 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.
In the coloring composition of the present invention, 60% by mass or more of the resin contained in the coloring composition is preferably the graft resin A, 65% by mass or more is preferably the graft resin A, and 70% by mass or more is the graft. Resin A is more preferable. Further, the upper limit can be, for example, 95% by mass or less, or 90% by mass or less. According to this aspect, the coating property of the coloring composition is good, and it is easy to form a film in which uneven thickness is suppressed.
In the coloring composition of the present invention, the content of the graft resin A is preferably 10 to 30% by mass in the total solid content of the coloring composition. The lower limit is more preferably 13% by mass or more, further preferably 15% by mass or more. The upper limit is more preferably 27% by mass or less, further preferably 25% by mass or less. According to this aspect, the coating property of the coloring composition is good, and it is easy to form a film in which uneven thickness is suppressed.
In the coloring composition of the present invention, the content of the graft resin A is preferably 30 to 90 parts by mass, more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the pigment (DPP). The lower limit is more preferably 40 parts by mass or more, and further preferably 45 parts by mass or more. The upper limit is more preferably 65 parts by mass or less, and further preferably 60 parts by mass or less. According to this aspect, the dispersibility of the pigment (DPP) in the coloring composition is good, and it is easy to form a film in which thickness unevenness is suppressed.
When the coloring composition of the present invention contains another resin in addition to the graft resin A, the content of the other resin is preferably 0 to 20% by mass in the total solid content of the coloring composition. The lower limit is more preferably 3% by mass or more, further preferably 5% by mass or more. The upper limit is more preferably 15% by mass or less, further preferably 13% by mass or less.

<< Polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated 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 less than 2000, 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 groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and 3 to 6 ethylenically unsaturated groups. More preferably, it is a compound containing an individual. 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.

The polymerizable compounds are dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon 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 (manufactured) NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. (For example, SR454, SR499 commercially available from Sartmer) are preferable. These oligomer types can also be used. Further, as the polymerizable compound, NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. Further, as the polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy-modified tri (meth) acrylate. It is also preferable to use a trifunctional (meth) acrylate compound such as 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, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.

The polymerizable compound may have an acid group. By using a polymerizable compound having an acid group, the colored composition layer in the unexposed portion can be easily removed during development, and the generation of development residue can be effectively 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 radically polymerizable compound having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like.

The acid value of the polymerizable compound having an acid group 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 more excellent developability can be obtained. When the acid value of the polymerizable compound is 40 mgKOH / g or less, it is advantageous in terms of production and handling.

As the polymerizable compound, a compound having a caprolactone structure is also a preferable embodiment. 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.

As the polymerizable compound, a compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups. More preferably, it is a 3-6 functional (meth) acrylate compound. Commercially available products of the polymerizable compound having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330 which is an acrylate.

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, it is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Commercially available products include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- Examples include 600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).
Further, as the polymerizable compound, it is also preferable to use 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
Further, as the polymerizable compound, the compounds described in Japanese Patent Application Laid-Open No. 2017-48367, Japanese Patent No. 6057891 and Japanese Patent No. 6031807 can also be used.

The content of the polymerizable compound is preferably 0.1 to 50% by mass based on 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 content of the polymerizable compound is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and 60 parts by mass or less with respect to 100 parts by mass of the above-mentioned graft resin A. Is more preferable. When the content of the polymerizable compound is within the above range, the dispersion of the pigment (DPP) in the composition is stable, and further excellent developability can be obtained.
The polymerizable compound may be used alone or in combination of two or more. When two or more kinds of polymerizable compounds are used in combination, it is preferable that the total of them is in the above range.

<< 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 reaction 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. Regarding the photopolymerization initiator, the description of paragraph numbers 0065 to 0111 of JP-A-2014-130173 and paragraph numbers 0274 to 0306 of JP-A-2013-29760 can be referred to, and these contents 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).

Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in the Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-66385, the compound described in JP-A-2000-66385. Compounds described in JP-A-2000-80068, compounds described in JP-A-2004-534977, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-197666, Patent No. Examples thereof include the compounds described in 1979/015596, the compounds described in WO2015 / 152153, and the compounds described in WO2017 / 051680. 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. As commercially available products of the oxime compound, 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 of JP2012-14052A) (all manufactured by ADEKA Corporation).

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. 7,626,957 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 in which a nitro group was introduced into the dye moiety, the keto-oxime compound described in International Publication No. WO2009 / 131189, and the same triazine skeleton and oxime skeleton. Using the compound described in US Pat. No. 7,556,910 contained in the molecule, the compound described in JP-A-2009-221114, which has a maximum absorption wavelength at 405 nm and has good sensitivity to a g-ray light source, and the like. May be good.

In the present invention, 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.

In the present invention, 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.

In the present invention, as the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication WO2013 / 083505.

In the present invention, 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.

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466, 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 range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. 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).

In the present invention, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator. Specific examples of such a photopolymerization initiator include paragraph numbers 0417 to 0421 of JP-A-2010-527339, JP-A-2011-524436, International Publication No. WO2015 / 004565, and JP-A-2016-532675. , International Publication WO2017 / 03368A, paragraph numbers 0039 to 0055, and the dimers of oxime compounds, and the compounds (E) and compounds (G) described in JP-A-2013-522445, International. Examples thereof include Cmpd1 to 7 described in Japanese Patent Publication No. WO2016 / 034963.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass based on 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 20% by mass or less, further preferably 10% by mass or less. The coloring composition 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.

<< 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). As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferable. The upper limit of the epoxy group is preferably 100 or less, more preferably 10 or less, and further preferably 5 or less.

The epoxy equivalent of the epoxy compound (= molecular weight of the compound having an epoxy group / number of epoxy groups) is preferably 500 g / eq or less, more preferably 100 to 400 g / eq, and 100 to 300 g / eq. It is more preferable to have.

The epoxy compound may be a small molecule 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 molecular weight of the epoxy compound (in the case of a polymer, the weight average molecular weight) is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the molecular weight (in the case of a polymer, the weight average molecular weight) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1500 or less.

Epoxy compounds are the compounds 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. 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 based on 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.

<< Solvent >>
The coloring composition of the present invention preferably 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-ethoxypropionic acid, 3-ethoxypropionic acid) (Ethyl etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionic acid, ethyl 2-alkyloxypropionic acid, propyl 2-alkyloxypropionic acid, etc. (eg, methyl 2-methoxypropionate) , 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl)), 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. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of improving solubility. The organic solvent may be used alone or in combination of two or more. 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 Methyl Ether, and Propylene Glycol Methyl Ether Acetate.

In the present invention, it is preferable to use a solvent having a low metal content as the solvent. The metal content in the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a 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, November 13, 2015). Day).

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

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

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.

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.

<< 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, amidine salt, amide compound (for example, above, for example. Japanese Patent Laid-Open No. 2013-41165, paragraph No. 0186), base generator (for example, ionic compound described in JP-A-2014-55114), isocyanate compound (eg, JP-A-2012-150180). Japanese Patent Laid-Open No. 0071), alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253504), onium salt compound (eg, JP-A-2015-34963). The compound exemplified as the acid generator in paragraph No. 0216, the 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 6.4% by mass in the total solid content of the coloring composition. % By mass is more preferred.

<< 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. As a specific example of the pigment derivative, for example, the description in paragraphs 0162 to 0183 of JP-A-2011-52065 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 of the thickness of the coating film and liquid saving property, and has good solubility in the 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 Co., 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.

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.

As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. For such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the content thereof is incorporated in the present specification.

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。As the fluorine-based surfactant, a block polymer can also be used. For example, the compounds described in JP-A-2011-89090 can be mentioned. 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. 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 an ethylenically unsaturated group 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 propoxylates, glycerol ethoxylates, 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 Junyaku) (Manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

Examples of the cationic surfactant include KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, No. 90, No. Examples include 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).

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), KP-341, 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.

<< UV absorber >>
The coloring composition of the present invention can contain an ultraviolet absorber. 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. Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available 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.

When the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, preferably 0.1 to 5% by mass, based on the total solid content of the coloring composition. More preferably, 0.1 to 3% by mass is particularly preferable. Further, as the ultraviolet absorber, only one kind may be used, or two or more kinds may be used. When two or more kinds of ultraviolet absorbers are contained, it is preferable that the total amount thereof is within 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 styrene 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). 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 10% by mass, based on the total solid content of the coloring composition. % 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 based on 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 solid content concentration of the coloring composition of the present invention is preferably 10 to 25% by mass. The upper limit is preferably 23% by mass or less, and more preferably 20% by mass or less. The lower limit is preferably 12% by mass or more, and preferably 14% by mass or more.

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, it is preferably 0.3 to 50 mPa · s, more preferably 0.5 to 20 mPa · s at 25 ° C. 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 coloring composition of the present invention uses a rotational viscometer and has a viscosity μ ₁ at 23 ° C. measured at a shear rate of 10s ^-1 and a viscosity μ at 23 ° C. measured at a shear rate 1000s ^-1 . It is preferable that μ ₂ / μ ₁ which is a ratio of ₂ is 0.75 or more and 1.25 or less. μ ₂ / μ ₁ is preferably 0.90 or more, and more preferably 0.95 or more. Further, μ ₂ / μ ₁ is preferably 1.10 or less, and more preferably 1.05 or less. When μ ₂ / μ ₁ is in the above range, the coatability is good and a film with suppressed thickness unevenness can be formed. As a method of adjusting μ ₂ / μ ₁ of the coloring composition to the above range, the solid content concentration of the coloring composition, the content of the pigment (DPP), the content of the graft resin A, and the like are appropriately adjusted. Can be adjusted to a range. For example, when it is desired to reduce μ ₂ / μ ₁ of the coloring composition within the above range, a method of lowering the solid content concentration of the coloring composition to about the lower limit of the above range can be mentioned. Further, when it is desired to increase μ ₂ / μ ₁ of the coloring composition within the above range, a method of increasing the solid content concentration of the coloring composition to about the upper limit within the above range can be mentioned.

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 as a composition for forming a colored layer in a color filter. In particular, it can be preferably used as a composition for forming a red colored layer of a color filter.

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.

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 perform the treatment 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 JP-A-2015-157893, "Practice of General Materials, 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 super). 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. (DFA4201NIEY, 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.

<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 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.

<Pattern formation method>
Next, the pattern forming method of the present invention will be described. The pattern forming method of the present invention includes a step of forming a coloring composition layer on a support using the coloring composition of the present invention described above, a step of exposing the coloring composition layer in a pattern (exposure step), and a step of exposing the coloring composition layer in a pattern. A step of developing and removing an unexposed portion of the coloring composition layer (development step) is included in this order. 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. For example, a glass substrate, a substrate for a solid-state image sensor provided with a solid-state image sensor (light receiving element) such as a CCD or CMOS, a silicon substrate, or the like can be mentioned. Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

Examples of the method for applying the coloring composition onto the support include a spin coating method, a slit coating method, an inkjet method, and the like, and the spin coating method is preferable because the effect of the present invention is more remarkably exhibited. The coating conditions in the spin coating method differ depending on the solid content concentration of the coloring composition and the like, but for example, spin coating is preferably performed at a rotation speed of 300 to 3000 rpm, and spin coating is performed at a rotation speed of 800 to 1500 rpm. Is more preferable. Within this range, it is easy to manufacture a cured film in which thickness unevenness is suppressed.

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 setting the prebake temperature 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, and for example, the illuminance may be 10,000 W / m ² when the oxygen concentration is 10% by volume, the illuminance may be 20000 W / m ² when the oxygen concentration is 35% by volume, and the like.

<< Development process >>
Next, the unexposed portion of the coloring composition layer is developed and removed to form a pattern. The development and removal of the unexposed portion of the coloring composition layer 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 developing solution, and only the photocured portion remains. 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, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and other organic alkaline compounds, and water. Examples thereof include inorganic alkaline compounds such as sodium oxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. 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. 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 preferable to perform heat treatment (post-baking) after development and drying. Post-baking is a post-development heat treatment for complete curing, and the heating temperature is preferably, for example, 100 to 240 ° C, more preferably 200 to 240 ° C. Further, when the support on which the cured film is formed includes an organic electroluminescence (organic EL) element, an image sensor having a photoelectric conversion film made of an organic material, and the like, the post-bake temperature is 150 ° C. or lower. Is preferable. The lower limit can be, for example, 50 ° C. or higher. Post-baking is performed by continuously or batch-type the developed film (cured film) using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high-frequency heater so as to meet the above conditions. It can be carried out.
The pattern forming method may include a process by dry etching. Examples of the dry etching process include the dry etching process described in paragraphs 0137 to 0165 of International Publication WO2018 / 061781.

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) Dimension 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 each 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).

<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. 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.

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

On the substrate, there are a plurality of photodiodes constituting the light receiving area of a solid-state image pickup device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to have a light-shielding film in which only the light-receiving part of the photodiode is open, and to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film. And has a color filter on the device protective film. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. There 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 by a partition wall, for example, in a grid pattern. 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 cured film 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 Devices (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Devices (Junaki Ibuki, Industrial Books). Co., Ltd. (issued in 1989) ”. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published 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 specifically described 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.

<Preparation of coloring composition>
[Preparation of coloring composition]
The raw materials shown below were stirred and mixed to prepare a colored composition. As the dispersion, the dispersion prepared as follows was used. In addition, the numerical values described in the column of PGMEA in the following table are numerical values including PGMEA contained in the dispersion liquid. The numerical values shown in the table below are parts by mass.

(Preparation of dispersion)
Pigments, pigment derivatives, and resins of the types listed in the dispersion column of the table below are mixed by parts by mass described in the dispersion column of the table below, and propylene glycol monomethyl ether acetate (PGMEA) is further added as a solvent. In addition, a mixed solution was prepared. 230 parts by mass of zirconia beads having a diameter of 0.3 mm was added to this mixed solution, and dispersion treatment was performed for 5 hours using a paint shaker. The beads were separated by filtration to produce a dispersion solution having a solid content concentration of 18% by mass.

The raw materials listed in the above table are as follows. The "content of graft resin A" in the above table has a poly (meth) acrylate structure as the main chain and a polyester structure graft chain as a side chain in the total mass of the resins contained in the coloring composition. It is a value of the content (mass%) of the graft resin (graft resin A) containing 20 mol% or more of the unit A.

(Pigment)
PR254: C.I. I. Pigment Red 254 (pigment represented by formula (DPP))
PR255: C.I. I. Pigment Red 255 (pigment represented by formula (DPP))
PR272: C.I. I. Pigment Red 272 (pigment represented by formula (DPP))
PO71: C.I. I. Pigment Orange 71 (pigment represented by formula (DPP))
PO73: C.I. I. Pigment Orange 73 (pigment represented by formula (DPP))
PY139: C.I. I. Pigment Yellow 139 (pigment other than the pigment represented by the formula (DPP))

(Pigment derivative)
B-1: Compound with the following structure

(resin)
C-1: Resin having the following structure (Mw = 20000, the numerical value added to the main chain is the molar ratio of the repeating unit, and the numerical value added to the side chain is the number of repeating units. C-1 is the above-mentioned graft resin. A.)
C-2: Resin having the following structure (Mw = 24000, the numerical value added to the main chain is the molar ratio of the repeating unit, and the numerical value added to the side chain is the number of repeating units. C-2 is the above-mentioned graft resin. A.)
C-3: Resin having the following structure (Mw = 11000, the numerical value added to the main chain is the molar ratio of the repeating unit).
C-4: Resin having the following structure (Mw = 22900, the numerical value added to the main chain is the molar ratio of the repeating unit).

(Alkali-soluble resin)
D-1: Resin C-3 described above

(Polymerizable compound)
E-1: NK Ester A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
E-2: Aronix TO-2349 (manufactured by Toagosei Co., Ltd.)
E-3: NK Ester A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

(Photopolymerization initiator)
F-1: IRGACURE-OXE01 (manufactured by BASF)
F-2: IRGACURE-OXE02 (manufactured by BASF)

(Surfactant)
G-1: The following compound (Mw = 14000). In the following formula,% indicating the ratio of the repeating unit is mol%.

(UV absorber)
H-1: UV-503 (manufactured by Daito Kagaku)

<Evaluation>
(Measurement of viscosity ratio μ ₂ / μ ₁ )
The colored composition immediately after preparation was measured at a shear rate of 1000 s ^-1 with respect to a viscosity of μ ₁ at 23 ° C. when measured at a shear rate of 10 s ^-1 using a rotational viscometer (MCR301, manufactured by Antonio Par). The ratio of viscosity μ ₂ at 23 ° C. (μ ₂ / μ ₁ ) was measured.

(Evaluation of uneven thickness)
On an 8 inch (20.32 cm) silicon wafer, a spin coat was applied to the colored composition using a spin coater so that the film thickness after prebaking was 0.64 μm (rotation speed = 1050 rpm), and then 100. Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at ° C. Then, it was further heated at 200 ° C. for 300 seconds using a hot plate to form a cured film.
Regarding the film thickness of the obtained cured film, 13 points of film thickness were measured at equal intervals in the outer circumference-center-outer circumference direction (diameter direction) of the 8-inch wafer using an optical film thickness meter (F50, manufactured by Filmometry). Then, the difference (Δt) between the maximum value and the minimum value of the film thickness was obtained. Thickness unevenness was evaluated using the value of Δt. The smaller Δt is, the smaller the thickness unevenness is.

As shown in the above table, in the examples, Δt was small and the thickness unevenness was suppressed. In particular, C.I. I. In Example 1 using Pigment Red 254, the thickness unevenness could be remarkably suppressed.

Claims (11)

A coloring composition containing Color Index Pigment Red 254, a resin, a photopolymerization initiator, and a polymerizable compound.
The content of Color Index Pigment Red 254 in the total solid content of the coloring composition is 35% by mass or more.
The resin has a poly (meth) acrylate structure as a main chain and a repeat having a graft chain having a structure represented by the formula (G-1), the formula (G-2) or the formula (G-3) in the side chain. It contains two types of graft resins containing 20 mol% or more of unit A and 60 mol% or more and 80 mol% or less of repeating units having an acid group.
60% by mass or more of the resin contained in the coloring composition is the graft resin, and the graft resin is used.
The content of the graft resin is 30 to 60 parts by mass with respect to 100 parts by mass of Color Index Pigment Red 254.
The coloring composition has a viscosity of μ ₁ at 23 ° C. as measured at a shear rate of 10 s ^-1 and a viscosity of μ ₂ at 23 ° C. as measured at a shear rate of 1000 s ^-1 using a rotational viscometer . The ratio μ ₂ / μ ₁ is 0.95 or more and 1.05 or less.
Coloring composition.

( ^RG1 represents an alkylene group, ^W100 represents an alkyl group or an alkoxy group having 5 to 24 carbon atoms, and n1 to n3 each independently represent an integer of 3 or more.) The coloring composition according to claim 1, wherein the graft chain contains a polyester structure derived from a compound selected from ε-caprolactone and δ-valerolactone. The coloring composition according to claim 1 or 2, wherein the repeating unit A has a weight average molecular weight of 1000 or more. The coloring composition according to any one of claims 1 to 3 , wherein the content of the graft resin is 15 to 25% by mass in the total solid content of the coloring composition. The coloring composition according to any one of claims 1 to 4 , wherein the polymerizable compound contains a polymerizable compound having an acid group. The coloring composition according to any one of claims 1 to 5 , wherein the content of the polymerizable compound is 100 parts by mass or less with respect to 100 parts by mass of the graft resin. A cured film obtained by curing the coloring composition according to any one of claims 1 to 6 . A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 6 .
The step of exposing the colored composition layer in a pattern and
The step of developing and removing the unexposed portion of the colored composition layer, and
Pattern forming method including. A color filter including the cured film according to claim 7 . The solid-state image sensor having the cured film according to claim 7 . An image display device having the cured film according to claim 7 .