TW201915099A - Colored composition, cured film, pattern formation method, color filter, solid imaging element, and image display device - Google Patents

Abstract

Provided is a colored composition which has satisfactory applicability and is capable of producing films reduced in thickness unevenness. Also provided are a cured film, a pattern formation method, a color filter, a solid imaging element, and an image display device. This colored composition comprises a given diketopyrrolopyrrole pigment, one or more resins, a photopolymerization initiator, and a polymerizable compound. The resins include a graft resin which comprises 20 mol% or more repeating unit A comprising: a poly(meth)acrylate structure as the main chain; and a branch of a polyester structure as a side chain. The graft resin accounts for 60 mass% or more of the resins contained in the colored composition.

Description

Coloring composition, cured film, pattern forming method, color filter, solid-state imaging element, and image display device

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 spread of digital cameras, mobile phones with cameras, and the like, the demand for solid-state imaging devices such as charge coupled device (CCD) image sensors has increased significantly. As a core device of a display or an optical element, a color filter is used. A color filter usually has pixels (coloring patterns) of three primary colors of red, green, and blue, and functions to decompose transmitted light into three primary colors.

For the coloring composition for forming a red pixel, a diketopyrrolopyrrole pigment such as a color index pigment red 254 is usually used. For example, Patent Documents 1 to 3 describe the production of a color filter using a coloring composition containing a color index pigment red 254. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2010-153872 (Patent Document 3) JP-A-2010-153872

However, the coating property of the colored composition containing the diketopyrrolopyrrole pigment is not sufficient, and the thickness unevenness tends to occur easily.

Accordingly, an object of the present invention is to provide a coloring composition which is excellent in coatability and which can produce a film in which thickness unevenness is suppressed. Further, a cured film, a pattern forming method, a color filter, a solid-state image sensor, and an image display device are provided.

As a result of intensive studies, the present inventors have found that the coating property of the coloring composition described later is good, and it is possible to produce a film in which thickness unevenness is suppressed, and the present invention has been completed. That is, the present invention is as follows. <1> A coloring composition comprising a pigment represented by the formula (DPP), a resin, a photopolymerization initiator, and a polymerizable compound, the resin comprising a graft resin containing 20 mol% or more of a polycondensation a repeating unit A having a (meth) acrylate structure as a main chain and having a graft chain of a polyester structure in a side chain, and 60% by mass or more of the resin contained in the coloring composition is a graft resin; Formula (DPP) [Chemical 1] Wherein R ¹ and R ² each independently represent 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, and m1 and m2 each independently represent an integer of 0 to 5, and when m1 is 2 or more, m1 R ^{1 's} may be the same, Alternatively, in the case where m2 is 2 or more, m2 R ^{2 's} may be the same or different. <2> The coloring composition according to <1>, wherein the pigment represented by the formula (DPP) is selected from the group consisting of color index pigment red 254, color index pigment red 255, color index pigment red 272, colorimetric index At least one of Pigment Orange 71 and Color Index Pigment Orange 73. <3> The coloring composition according to <1> or <2>, wherein the graft chain is a structure represented by the formula (G-1), the formula (G-2) or the formula (G-3); 2] R ^G1 represents an alkylene group, and W ¹⁰⁰ represents a hydrogen atom or a substituent. N1 to n3 each independently represent an integer of 3 or more. The colored composition according to any one of <1> to <3> wherein the graft chain comprises a polyester structure derived from a compound selected from the group consisting of ε-caprolactone and δ-valerolactone. The colored composition according to any one of <1> to <4> wherein the weight average molecular weight of the repeating unit A is 1,000 or more. The colored composition according to any one of <1> to <5> wherein the polymerizable compound contains a polymerizable compound having an acid group. The coloring composition according to any one of the above aspects, wherein the content of the polymerizable compound is 100 parts by mass or less based on 100 parts by mass of the graft resin. The colored composition according to any one of the above-mentioned items, wherein the content of the graft resin is from 30 to 90 parts by mass based on 100 parts by mass of the pigment represented by the formula (DPP). <9> The coloring composition according to any one of <1> to <8>, wherein a viscosity μ ₂ at 23 ° C and a shearing at a shear rate of 1000 s ^-1 using a rotational viscometer are used. The ratio of the viscosity μ ₁ at 23 ° C measured at a speed of 10 s ^-1 , that is, μ ₂ /μ ₁ is 0.75 or more and 1.25 or less. <10> A cured film obtained by curing the colored composition according to any one of <1> to <9>. <11> A pattern forming method, comprising: a step of forming a colored composition layer on a support using the coloring composition according to any one of <1> to <9>; exposing the colored composition layer to a pattern a step of forming; and developing the step of removing the unexposed portion of the colored composition layer. <12> A color filter comprising the cured film according to <10>. <13> A solid-state image sensor having the cured film according to <10>. <14> An image display device comprising the cured film according to <10>. [Effect of the invention]

According to the present invention, it is possible to provide a coloring composition which is excellent in coatability and which can produce a film in which thickness unevenness is suppressed. Further, it is possible to provide a cured film, a pattern forming method, a color filter, a solid-state image sensor, and an image display device.

Hereinafter, the contents of the present invention will be described in detail. In the label of the group (atomic group) in the present specification, the unlabeled and unsubstituted label is not labeled to include a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the term "exposure" means not only the exposure using light but also the drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified. In addition, as the light used for the exposure, active light rays or radiation such as far-line ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams typified by a bright line spectrum of a mercury lamp and an excimer laser are generally used. In the present specification, the numerical range expressed by "to" means a range including the numerical values described before and after "to" as the lower limit and the upper limit. In the present specification, the total solid content means the total mass of the components from which the solvent is removed from all the components of the composition. In the present specification, infrared refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm. In the present specification, "(meth) acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid," (Methyl)allyl" means either or both of allyl and methallyl, and "(meth)acryloyl" means both an acryloyl group and a methacryloyl group. One. In the present specification, the term "step" includes not only independent steps but also includes the intended function of the step in the case where it cannot be clearly distinguished from other steps. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, the term "pigment" means an insoluble pigment compound which is difficult to dissolve in a solvent. The pigment used in the present invention is preferably, for example, a dissolved amount of 100 g of propylene glycol monomethyl ether acetate at 25 ° C and a dissolved amount of 0.1 g or less at 25 ° C relative to 100 g of water, preferably 0.05 g. The following is more preferable, and 0.01 g or less is further preferable.

The colored composition of the present invention comprises a pigment represented by the formula (DPP), a resin, a photopolymerization initiator, and a polymerizable compound, which are characterized in that the resin comprises a graft resin, and the graft resin comprises 20 The repeating unit A having a poly(meth)acrylate structure having a poly(meth)acrylate structure as a main chain and having a polyester structure in a side chain, and 60% by mass or more of the resin contained in the coloring composition is the above Graft resin.

According to the study by the present inventors, it has been found that the diketopyrrolopyrrole pigment has a relatively high tendency of interaction between pigments, and the viscosity of the colored composition containing the diketopyrrolopyrrole pigment greatly decreases as the shear rate increases. The tendency of the viscosity to change with respect to the shear rate is large. Since the colored composition containing the diketopyrrolopyrrole pigment has such a viscosity characteristic, it is presumed that thickness unevenness is likely to occur. For example, in the case of spin-coating a colored composition containing a diketopyrrolopyrrole pigment, the centrifugal force becomes stronger as it moves away from the center of rotation, and therefore the film thickness near the center of rotation is likely to be thicker than that of the outer periphery, and as a result, it is estimated It is prone to uneven thickness. The colored composition of the present invention contains a pigment represented by the formula (DPP) (hereinafter, also referred to as a pigment (DPP)) and contains 60% by mass or more of the above specific repeating unit A containing 20 mol% or more. Since the resin of the graft resin is small, the interaction between the pigments (DPP) in the colored composition is small, and the dispersibility of the pigment (DPP) is good, so the amount of change in viscosity with respect to the shear rate is small, and as a result, it is presumed that it is coated. The film is good and can produce a film in which thickness unevenness is suppressed. Therefore, the coloring composition of the present invention has good coatability and can produce a film in which thickness unevenness is suppressed.

At least one selected from the group consisting of color index index pigment red 254, color index index pigment red 255, color index index pigment red 272, colorimetric index pigment orange 71, and colorimetric index pigment orange 73 is used as the pigment in the coloring composition ( In the case of DPP), the effect of improving the thickness unevenness is remarkably exhibited, and in the case where the color index pigment red 254 is used as the pigment (DPP), the effect of improving the thickness unevenness is further remarkably exhibited.

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

<<Pigment represented by formula (DPP)>> The coloring composition of the present invention contains a pigment represented by the formula (DPP). The pigment is a pigment having a diketopyrrolopyrrole skeleton. Hereinafter, the pigment represented by the formula (DPP) is also referred to as a pigment (DPP). Formula (DPP) [Chemical 3] Wherein R ¹ and R ² each independently represent 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, and m1 and m2 each independently represent an integer of 0 to 5, and when m1 is 2 or more, m1 R ^{1 's} may be the same, Alternatively, in the case where m2 is 2 or more, m2 R ^{2 's} 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 alkyl group represented by R ¹ , R ² , R ^D1 and R ^D2 has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain, and a straight chain or a branched chain is preferred. The alkyl group may have a substituent. The substituent which is mentioned in the substituent T mentioned later is mentioned as a substituent.

The carbon number of the aryl group represented by R ^D1 and R ^D2 is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 12. The aryl group may have a substituent. The substituent which is mentioned in the substituent T mentioned later is mentioned as a substituent. The heteroaryl group represented by R ^D1 and R ^D2 may be a single ring or a fused ring. The number 1 to 3 of the hetero atom of the ring constituting the heteroaryl group is preferred. The hetero atom of the ring constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. A heteroaryl group of 5 rings or 6 rings is preferred. The number of carbon atoms of the ring constituting the heteroaryl group is preferably from 3 to 30, more preferably from 3 to 18, still more preferably from 3 to 12. The heteroaryl group may have a substituent. The substituent which is mentioned in the substituent T mentioned later is mentioned as a substituent.

R ¹ and R ² are each independently a halogen atom, an alkyl group or a cyano group, and a halogen atom or an alkyl group is more preferable, and a halogen atom is further preferable.

M1 and m2 each independently represent an integer of 0 to 5, an integer of 0 to 2 is preferable, and 0 or 1 is more preferable.

The substituent T is exemplified by 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), or an aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amine group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), and an aryloxy group. a base (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group, a fluorenyl group (preferably a fluorenyl group having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably having a carbon number of 2 to 30) Alkoxycarbonyl), aryloxycarbonyl (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), a heteroaryloxycarbonyl group, a decyloxy group (preferably a decyloxy group having 2 to 30 carbon atoms), hydrazine An amine group (preferably a decylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), or an aryloxycarbonylamino group (preferably An aryloxycarbonylamino group having 7 to 30 carbon atoms, an aminesulfonyl group (preferably an amidoxime group having a carbon number of 0 to 30), an amine formazan group (preferably an amine formazan having a carbon number of 1 to 30) Base), alkylthio group (preferably alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroaromatic sulfur (preferably having a carbon number of 1 to 30), an alkylsulfonyl group (preferably having a carbon number of 1 to 30), an arylsulfonyl group (preferably having a carbon number of 6 to 30), and a heteroarylsulfonyl group ( Preferred is a carbon number of 1 to 30), an alkylsulfinylene group (preferably having a carbon number of 1 to 30), an arylsulfinyl group (preferably having a carbon number of 6 to 30), and a heteroarylsulfinium sulfonium. Base (preferably having a carbon number of 1 to 30), a urea group (preferably having a carbon number of 1 to 30), a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, a carboxylic acid oxime group, a sulfonate sulfonium group, and a quinone imine. An acid group, a mercapto group, a halogen atom, a cyano group, an alkylsulfinic acid group, an arylsulfinic acid group, a fluorenyl group, an imido group, or a heteroaryl group (preferably having a carbon number of 1 to 30). In the case where the groups are groups which are also capable of being substituted, they may have a substituent. The substituent described in the above substituent T is exemplified as the substituent.

Specific examples of the pigment (DPP) include compounds having the following structures. In the following table, in the case where the substituent is represented by "-", it is represented as a hydrogen atom. For example, DPP-1 represents a compound in which Z ¹ , Z ³ to Z ¹⁰ are a hydrogen atom and Z ² is -OCH ₃ . Further, Me represents a methyl group, and Ph represents a phenyl group.

[Table 1]

[Table 2]

[table 3]

[Chemical 4]

Among the compounds of the above structure, the compound PR254 is a colorimetric index (CI) pigment red 254, the compound PR255 is a CI pigment red 255, the compound PR272 is a CI pigment red 272, the compound PO71 is a CI pigment orange 71, and the compound PO73 is a CI pigment orange 73. .

In the present invention, as the pigment (DPP), colorimetric index (CI) pigment red 254, CI pigment red 255, CI pigment red 272, CI pigment orange 71, and CI pigment orange 73 are preferable, and the thickness can be further remarkably suppressed. For the same reason, CI Pigment Red 254 is more preferred.

The content of the pigment (DPP) is preferably 30% by mass or more based on the total solid content of the coloring composition, more preferably 33% by mass or more, and still more preferably 35% by mass or more. The upper limit can be set to 55 mass% or less. In addition, the ratio of the pigment (DPP) in the total mass of the coloring agent contained in the coloring composition is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more. The upper limit can be set to 100% by mass or less.

<<Other Coloring Agent>> 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). Other colorants may be pigments or dyes. It is also possible to use both pigments and dyes. The coloring agent used in the present invention preferably contains a pigment. Further, the content of the pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Also, the colorant may be only a pigment.

Examples of the pigment include inorganic pigments and organic pigments, and organic pigments are preferred. Examples of the organic pigment include the following.

CI Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36 , 36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97 ,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139 ,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179 , 180,181,182,185,187,188,193,194,199,213,214, etc. (above yellow pigment), CI Pigment Orange 2,5,13,16,17:1,31,34,36 , 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, etc. (above orange pigment), CI pigment red 1, 2, 3, 4, 5, 6, 7 , 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52 : 2, 53:1, 57:1, 60:1, 63:1, 66, 6 7, 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. (the above are red pigments); CI pigment green 7,10, 36, 37, 58, 59 (the above are green pigments), CI pigment violet 1,19,23,27,32,37, 42 et al (above purple pigment), CI pigment blue 1,2,15,15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (above is blue pigment).

Further, as the green pigment, a zinc halide phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can be used. Specific examples include the compounds described in WO 2015/118720. Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraphs 0047 of JP-A-2011-157478.

The dye is not particularly limited, and a known dye can be used. As the chemical structure, a pyrazole azo type, an anilino azo type, a triarylmethane type, an anthraquinone type, an anthrapyridone type, a benzylidene type, an oxaphthalocyanine type, and a pyrazolotriazole azo can be used. , pyridone azo, cyanine, thiophene, pyrrolopyrazole methine azo, xanthene, phthalocyanine, benzopyran, indigo, A dye such as pyrrole methylene. In addition, the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, and JP-A-2011-145540 can be preferably used. Azo compound. In addition, as the yellow dye, the quinophthalone compound described in paragraphs 0011 to 0034 of JP-A-2013-054339, and the paragraphs 0013 to 0058 of JP-A-2014-026228 can be used. Quinoline yellow compound and the like.

Further, as another coloring agent, a dye polymer can also be used. The dye polymer is preferably a dye which is dissolved in a solvent, but the dye polymer can form particles. When the dye polymer is a particle, it is usually used in a state of being dispersed in a solvent. The pigment polymer in the form of a particle can be obtained, for example, by emulsion polymerization, and a compound and a production method described in JP-A-2015-214682 are exemplified as 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 it can also be set to 100 or less. The plurality of pigment structures in one molecule may be the same pigment structure or different pigment structures. The weight average molecular weight (Mw) of the dye polymer is preferably from 2,000 to 50,000. The lower limit is preferably 3,000 or more, and more preferably 6,000 or more. The upper limit is preferably 30,000 or less, and more preferably 20,000 or less. As the dye-polymer, the compound described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, and the like can be used. .

The other coloring agent is preferably a yellow coloring agent, more preferably a yellow pigment, and one or more selected from the group consisting of CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185 is further preferably selected from CI Pigment Yellow 139 and One or more of CI Pigment Yellow 185 is still more preferable, and CI Pigment Yellow 139 is particularly preferable. In this way, it is easy to obtain more excellent coating properties. Moreover, spectral characteristics which are preferable in terms of color reproducibility can be obtained.

In the case where the colored composition of the present invention contains other coloring agents (that is, a coloring agent other than the pigment (DPP)), the content of the other coloring agent is 10 to 100 masses with respect to 100 parts by mass of the pigment (DPP). The serving is preferred. The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. The upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less. Further, the content of the yellow colorant is preferably 10 to 100 parts by mass based on 100 parts by mass of the pigment (DPP). The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. The upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less. Further, the total content of the pigment (DPP) and other coloring agents is preferably from 30 to 70% by mass based on 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 mass% or less, more preferably 60 mass% or less. Further, the total content of the pigment (DPP) and the yellow colorant is preferably from 30 to 70% by mass based on 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 mass% or less, more preferably 60 mass% or less.

<<Resin>> The coloring composition of the present invention contains a resin. In the present invention, the term "resin" means an organic compound other than a colorant and has an organic compound having a molecular weight of 2,000 or more. The resin is blended, for example, by using a particle such as a pigment in a composition and a use of a binder. Further, a resin mainly used for dispersing particles of a pigment or the like is also referred to as a dispersant. However, such use of the resin is an example, and it can also 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.

(Grafted Resin A) The colored composition of the present invention contains a graft resin (hereinafter, also referred to as graft resin A) as a resin, and the graft resin contains 20 mol% or more of poly(meth)acrylate. The repeating unit A having a structure as a main chain and having a graft chain of a polyester structure on a side chain. The graft resin A can be preferably used as a dispersant for a pigment (DPP). In the present specification, the term "grafted resin" means a resin having a graft chain. Further, the graft chain means the end from the root of the main chain of the polymer to the group branched by the autonomous chain.

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

In the present invention, the graft chain in the graft resin A means a polymer chain branched and extended from the main chain of the repeating unit. The length of the graft chain is not particularly limited, and if the graft chain is elongated, the steric repellency effect is increased, and the dispersibility of the pigment (DPP) can be improved. As the graft chain, the number of atoms other than the hydrogen atom is preferably from 40 to 10,000, the number of atoms other than the hydrogen atom is more preferably from 50 to 2,000, and the number of atoms other than the hydrogen atom is more preferably from 60 to 500.

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

The graft chain may be a structure represented by the formula (G-1), the formula (G-2) or the formula (G-3). [Chemical 5] R ^G1 represents an alkylene group, and W ¹⁰⁰ represents a hydrogen atom or a substituent. N1 to n3 each independently represent an integer of 3 or more.

The carbon number of the alkylene group represented by R ^G1 is preferably from 1 to 20, more preferably from 2 to 16, and further preferably from 3 to 12. The alkyl group is preferably linear or branched, and more preferably linear.

N1 to n3 each independently represent an integer of 3 or more, more preferably 4 or more, and still more preferably 5 or more. The upper limit is preferably 100 or less, more preferably 80 or less, and still more preferably 60 or less.

W ¹⁰⁰ represents a hydrogen atom or a substituent. The substituent may, for example, be an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group or a heteroaryl sulfide group. Among them, from the viewpoint of improving the dispersibility of the pigment (DPP), a group having a steric repellency effect is preferred, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferred. The alkyl group and the alkoxy group may be any of a linear chain, a branched chain, and a cyclic chain, and a linear or branched form is preferred.

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 the group consisting of ε-caprolactone and δ-valerolactone. The polyester structure derived from ε-caprolactone includes a structure represented by the following ε-CL. The polyester structure derived from δ-valerolactone includes a structure represented by the following δ-VL. [Chemical 6]

The above repeating unit A in the graft resin A is preferably a repeating unit represented by the following formula (GA). Formula (GA) [Chem. 7]

Wherein R ^A1 represents a hydrogen atom or an alkyl group, L ^A1 represents a single bond or a divalent linking group, and W ^A1 represents a graft chain of a polyester structure.

The alkyl group represented by R ^A1 has preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 carbon atom. R ^A1 is preferably a hydrogen atom or a methyl group.

The divalent linking group represented by L ^A1 may, for example, be an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) or an extended aryl group (preferably an extended aryl group having 6 to 20 carbon atoms). And -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and a group obtained by combining two or more of them. The alkylene group may be any of a linear chain, a branched chain, and a cyclic chain, and is preferably a linear chain or a branched chain.

W ^A1 represents a graft chain of a polyester structure. The graft chain of the polyester structure is preferably a graft chain of the above formula (G-1), formula (G-2) or formula (G-3).

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 10,000, still more preferably 1,000 to 7,500. Further, 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 of the repeating unit A. For example, the repeating unit A can be formed by polymerizing a macromonomer. Here, the macromonomer refers to a polymer compound having a polymerizable group introduced at the end of the polymer. In the case where the macromonomer is used to form the repeating unit A, 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 more preferably 23 mol%. The above is further preferred. The upper limit can be set to 100% by mole, and can be set to 90% by mole or less, and can be 80% by mole or less, 70% by mole or less, or 60% by mole or less.

The graft resin A used in the present invention may further contain a repeating unit other than the above 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. The polymerizable group may, for example, be an ethylenically unsaturated group such as a vinyl group, a (meth)allyl group or a (meth)acryloyl group.

The graft resin A further contains a repeating unit having an acid group, and imparts alkali developability, and an effect of improving the resolution can be expected. In addition, the graft resin A further contains a repeating unit having a polymerizable group, and a cured film excellent in various physical properties such as heat resistance can be easily obtained.

In the case where the graft resin A contains a repeating unit having an acid group, in all the repeating units of the graft resin A, the content of the repeating unit having an acid group is preferably from 50 to 80 mol%. The lower limit is preferably 55 mol% or more, and more preferably 60 mol% or more. The upper limit is preferably 78 mol% or less, and more preferably 77 mol% or less. In the case where the graft resin A contains a repeating unit having a polymerizable group, in all the repeating units of the graft resin A, the content of the repeating unit having a polymerizable group is preferably 10 to 40 mol%. 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 resins having the following structures. Further, the graft resin A can be referred to in paragraphs 0025 to 0094 of JP-A-2012-255128, and the contents are incorporated in the present specification. [化8]

(Other Resin) The colored composition of the present invention may further contain a resin other than the above-described graft resin A (hereinafter also referred to as another resin). Examples of the other resin include a resin (linear organic polymer) having no graft chain. An example of another resin is an alkali-soluble resin.

The alkali-soluble resin can be appropriately selected from resins having a group which promotes alkali dissolution. The group which promotes alkali dissolution (hereinafter, also referred to as an acid group) may, for example, be a carboxyl group, a phosphoric acid group, a sulfo group or a phenolic hydroxyl group, and a carboxyl group is preferred. The type of the acid group of the alkali-soluble resin may be one type or two or more types.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 100,000. Further, the number average molecular weight (Mn) of the alkali-soluble resin is preferably from 1,000 to 20,000.

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of heat resistance. Further, from the viewpoint of suppressing developability, an acrylic resin, an acrylamide resin, and an acrylic acid/acrylamide copolymerized resin are preferable.

The alkali-soluble resin is preferably a polymer having a carboxyl group in a side chain. For example, it may be derived from methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth)acrylic acid, vinylbenzoic acid, partially esterified butylene A copolymer of a repeating unit such as an acid; an alkali-soluble phenol resin such as a novolac type resin; an acidic cellulose derivative having a carboxyl group in a side chain; and a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include (meth) methacrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). ) butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (methyl) Benzyl acrylate, tri(meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrafluorodecyl methacrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, and polymethylmethacrylic acid. Ester macromonomers, etc. Further, examples of the other monomer include an N-substituted maleimide monomer such as N-phenylmaleimide or N-cyclohexylmethyleneimine. These other monomers which can be copolymerized with (meth)acrylic acid may be used alone or in combination of two or more.

As the alkali-soluble resin, a benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid 2-hydroxyethyl group can be preferably used. A multi-copolymer of an ester copolymer, benzyl (meth)acrylate/(meth)acrylic acid/other monomer. In addition, 2-hydroxyethyl (meth)acrylate described in JP-A-7-140654, which is obtained by copolymerizing 2-hydroxyethyl (meth)acrylate with another monomer, can also be preferably used. Ester/Polystyrene Macromer/Benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethylmethacrylate macromer/methacrylic acid Benzyl ester/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polyphenylene Ethylene macromonomer / benzyl methacrylate / methacrylic acid copolymer. In addition, as a commercial item, for example, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.) or the like can be used.

The alkali-soluble resin can also use an alkali-soluble resin having a polymerizable group. Examples of the polymerizable group include a (meth)allyl group and a (meth)acrylonitrile group. The alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin having a polymerizable group in a side chain. As a commercially available product of the alkali-soluble resin having a polymerizable group, a DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.) and Photomer 6173 (a carboxyl group-containing polyurethane acrylate oligomer) are used. Diamond Shamrock Co., Ltd., VISCOAT R-264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), and PLACCEL CF200 series (all manufactured by Daicel Corporation), Ebecry l3800 (manufactured by DAICEL UCB CO., LTD.), ACRYCURE RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), DP-1305 (manufactured by FUJIFILM Fine Chemicals Co., Ltd.), and the like.

The alkali-soluble resin is preferably a polymer containing at least one selected from the group consisting of a compound represented by the following formula (ED1) and a compound represented by the formula (1): JP-A-2010-168539. The monomer components of the various compounds (hereinafter, these compounds are also referred to as "ether dimers") are polymerized.

[Chemistry 9]

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

Specific examples of the ether dimer include the compounds described in Paragraph No. 0317 of JP-A-2013-029760, and the contents are incorporated herein by reference. The ether dimer may be used alone or in combination of two or more.

Examples of the polymer obtained by polymerizing a monomer component containing an ether dimer include a polymer having the following structure. [化10]

The alkali-soluble resin may further contain a repeating unit derived from a compound represented by the following formula (X). [11] In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may include a benzene ring. n represents an integer of 1 to 15.

In the above formula (X), the alkyl group of R ₂ has preferably 2 to 3 carbon atoms. Further, the alkyl group of R ₃ has preferably 1 to 10 carbon atoms. The alkyl group of R ₃ may also 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 descriptions of paragraphs 0558 to 0571 of the Japanese Patent Application Laid-Open No. 2012-208494 (paragraphs 0685 to 0700 of the specification of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents are incorporated. In this manual. In addition, the copolymer (B) described in paragraphs 0029 to 0063 of JP-A-2012-032767 and the alkali-soluble resin used in the examples, and the paragraph number of JP-A-2012-208474 can be used. The adhesive resin described in 0088 to 0098 and the adhesive resin used in the examples, and the adhesive resin described in paragraphs 0022 to 0032 of JP-A-2012-137531, and the adhesives used in the examples. The binder resin described in paragraphs 0132 to 0143 of JP-A-2013-024934, and the binder resin used in the examples, and paragraphs 0092 to 0098 of JP-A-2011-242752 and The adhesive resin used in the examples, and the adhesive resin described in paragraphs 0030 to 0072 of JP-A-2012-032770. These contents are incorporated in this specification.

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

In the colored composition of the present invention, the content of the resin in the total solid content of the colored composition is preferably from 1 to 80% by mass. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, and more 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 the graft resin A, and 65 mass% or more is preferably the graft resin A, and 70% by mass or more is the graft. Resin A is further preferred. In addition, the upper limit can be, for example, 95% by mass or less, and can be 90% by mass or less. In this way, the coating property of the colored composition is good and it is easy to form a film in which thickness unevenness is suppressed. In the coloring composition of the present invention, the content of the graft resin A is preferably from 10 to 30% by mass based on the total solid content of the coloring composition. The lower limit is preferably 13% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 27% by mass or less, more preferably 25% by mass or less. In this way, the coating property of the colored composition is good and it is easy to form a film in which thickness unevenness 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, and more preferably 30 to 70 parts by mass, based on 100 parts by mass of the pigment (DPP). The lower limit is more preferably 40 parts by mass or more, and more preferably 45 parts by mass or more. The upper limit is more preferably 65 parts by mass or less, and more preferably 60 parts by mass or less. In this manner, the pigment (DPP) in the colored composition has good dispersibility and is easy to form a film in which thickness unevenness is suppressed. In the case where the coloring composition of the present invention contains other resin in addition to the graft resin A, the content of the other resin is preferably 0 to 20% by mass based on the total solid content of the coloring composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 13% by mass or less.

<<Polymerizable Compound>> The colored composition of the present invention contains a polymerizable compound. The polymerizable compound may, for example, be a compound having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

The polymerizable compound may be any of a chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferred. The molecular weight of the polymerizable compound is preferably less than 2,000, more preferably 1,500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more.

The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and still more preferably contains 3 to 6 ethylene groups. A compound of an unsaturated group. Further, the polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, more preferably a 3- to 6-functional (meth) acrylate compound. Specific examples of the polymerizable compound include paragraphs 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, and paragraph 0254 of JP-A-2008-292970. The compounds described in ～ 0257, and these contents are incorporated in the present specification.

The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co.). , manufactured by Ltd., dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (as a commercial product) It is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., manufactured by NK ESTER A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) and bonded via ethylene glycol and/or propylene glycol residues. A compound having a structure of an acrylonitrile group (for example, SR454, SR499 commercially available from SARTOMER Company, Inc.) is preferred. Moreover, these oligomer types can also be used. Further, as the polymerizable compound, NK ESTER A-TMMT (manufactured by Shin-Nakamura Chemical 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 propylene oxide-modified tris(meth)acrylate, trimethylolpropane oxirane were used. A trifunctional (meth) acrylate compound such as tris(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth) acrylate or pentaerythritol tri(meth) acrylate is also preferred. Commercial products of a trifunctional (meth) acrylate compound include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-. 306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A -TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 ( Nippon Kayaku Co., Ltd.) and the like.

The polymerizable compound may have an acid group. By using a polymerizable compound having an acid group, the coloring composition layer in the unexposed portion can be easily removed during development, and the development residue can be effectively suppressed. The acid group may, for example, be a carboxyl group, a sulfo group or a phosphoric acid group, and a carboxyl group is preferred. As a commercial item of the radical-polymerizable compound which has an acid group, ARONIX M-510, M-520, ARONIX TO-2349 (made by TOAGOSEI CO., LTD.), etc. are mentioned.

The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH/g, more preferably from 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the solubility with respect to the developer is good, and further excellent developability can be obtained. If the acid value of the polymerizable compound is 40 mgKOH/g or less, it is advantageous for production or handling.

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

As the polymerizable compound, a compound having an alkoxy group can also be used. The polymerizable compound having an alkoxy group is preferably a compound having an ethyloxy group and/or a propyloxy group, and a compound having an ethyloxy group is more preferable, and has 4 to 20 ethyl groups. A 3- to 6-functional (meth) acrylate compound of an oxy group is further preferred. As a commercial product of the polymerizable compound having an alkoxy group, for example, a tetrafunctional (meth) acrylate having four ethylene groups, that is, SR-494, which is manufactured by SARTOMER Company, Inc., has Three trifunctional (meth) acrylates which are isobutoxy groups are also known as KAYARAD TPA-330.

As the polymerizable compound, for example, as described in JP-A-48-041708, JP-A-51-037193, JP-A-2-032293, JP-A-2-016765, Ethylene acrylates are described in JP-A-58-049860, JP-A-56-017654, JP-A-62-039654, JP-A-62-039417, and JP-A-62-039418. A skeleton urethane compound is also preferred. Further, a polymerizable compound having an amine group structure or a thioether structure in a molecule described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Also preferred. As a commercial item, UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Further, as the polymerizable compound, 8UH-1006, 8UH-1012 (the above is manufactured by TAISEI FINE CHEMICAL CO., LTD.), LIGHTACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co., LTD.), or the like is also preferably used. In addition, as the polymerizable compound, a compound described in JP-A-H08-A No. 0, 074, 807, and Japanese Patent No. 6031807 can be used.

The content of the polymerizable compound is preferably from 0.1 to 50% by mass based on the total solid content of the coloring composition. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. In addition, the content of the polymerizable compound is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 60 parts by mass or less, based on 100 parts by mass of the graft resin A. When the content of the polymerizable compound is within the above range, the dispersion of the pigment (DPP) in the composition is stabilized, and further excellent developability can be obtained. The polymerizable compound may be used alone or in combination of two or more. In the case where two or more kinds of polymerizable compounds are used at the same time, the total of them is preferably 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 polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferred. Further, it may be a compound which generates a certain action with a photo-excited sensitizer and generates an active radical.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, a compound having a three-well skeleton, a compound having an oxadiazole skeleton, etc.), a mercaptophosphine compound, a hexaarylbisimidazole, an anthraquinone compound, and an organic compound. A peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, an α-hydroxyketone compound, an α-aminoketone compound, or the like. The photopolymerization initiator is a trihalo methyl triazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, or a mercapto group from the viewpoint of exposure sensitivity. Phosphine compound, phosphine oxide compound, metallocene compound, hydrazine compound, triarylimidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron a halomethyl oxadiazole compound and a 3-aryl substituted coumarin compound are preferred, and the compound selected from the group consisting of an anthraquinone compound, an α-hydroxyketone compound, an α-aminoketone compound, and a mercaptophosphine compound is More preferably, the hydrazine compound is further preferred. For the photopolymerization initiator, the descriptions of paragraphs 0065 to 0110 of JP-A-2014-130173, and paragraphs 0274 to 0306 of JP-A-2013-029760 can be referred to, and the contents are incorporated in the specification. .

The commercially available product of the α-hydroxyketone compound may, for example, be IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF Corporation). The commercially available product of the α-amino ketone compound may, for example, be IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF Corporation). The commercially available product of the mercaptophosphine compound may, for example, be IRGACURE-819 or DAROCUR-TPO (above, manufactured by BASF Corporation).

For example, the compound described in JP-A-2001-233068, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166, Compounds described in JCS Perkin II (1979, pp. 1653-1660), JCS Perkin II (1979, pp. 156-162), Journal of Photopolymer Science And the compound described in Japanese Patent Laid-Open Publication No. 2000-066385, and the compound described in JP-A-2000-080068, JP-A No. 2000-080068 The compound described in JP-A-2006-342166, the compound described in JP-A-H09-019766, and the compound described in Japanese Patent No. 6065596 The compound described in the publication of WO 2015/152153, and the compound described in the publication WO 2017/051680. Specific examples of the hydrazine compound include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3-propoxycarbonyl group. Iminobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-phenyl醯oxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimido- 1-phenylpropan-1-one and the like. As a commercial product of a ruthenium compound, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, manufactured by BASF Corporation) can also be preferably used. Further, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (CHANCZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADEKA ARKLS NCI-930, ADECA OPTOMER N-1919 ( The photopolymerization initiator 2) (above, ADEKA CORPORATION) described in Japanese Laid-Open Patent Publication No. 2012-014052.

In addition, as the ruthenium compound other than the above, a compound described in JP-A-2009-519904, in which N is bonded to the N-position of the carbazole ring, and a hetero substituent introduced into the benzophenone moiety can be used. The compound described in the U.S. Patent No. 7,626,957, the compound of the Japanese Patent Publication No. 2010-015025, and the Japanese Patent Publication No. 2009-0292039, and the International Publication No. WO2009/131189 The ketone oxime compound described in the above, the compound described in U.S. Patent No. 7,569,910, which contains three well skeletons and an anthracene skeleton in the same molecule, and the Japanese ray having a maximum absorption wavelength at 405 nm and having good sensitivity to a g-ray source. The compound or the like described in JP-A-2009-221114 is opened.

In the present invention, as the photopolymerization initiator, an anthracene compound having an anthracene ring can also be used. Specific examples of the ruthenium compound having an anthracene ring include the compounds described in JP-A-2014-137466. This content is incorporated in this specification.

In the present invention, as the photopolymerization initiator, an anthracene compound having a benzofuran skeleton can also be used. Specific examples include the compounds OE-01 to OE-75 described in WO 2015/036910.

Further, in the present invention, a ruthenium compound having at least one benzene ring having a carbazole ring as a skeleton of a naphthalene ring can be used as a photopolymerization initiator. Specific examples of the ruthenium compound include the compounds described in WO 2013/083505.

In the present specification, as the photopolymerization initiator, a ruthenium compound having a fluorine atom can also be used. Specific examples of the ruthenium compound having a fluorine atom include the compounds described in JP-A-2010-262028, and the compounds 24 and 36 to 40 described in JP-A-2014-500852. Compound (C-3) or the like described in Japanese Patent Publication No. 2013-164471. This content is incorporated in this specification.

In the present specification, as the photopolymerization initiator, a ruthenium compound having a nitro group can be used. It is also preferred that the ruthenium compound having a nitro group be a dimer. Specific examples of the ruthenium compound having a nitro group include those described in paragraphs 0031 to 0047 of JP-A-2013-114249 and paragraphs 0008 to 0102 and 0070 to 0079 of JP-A-2014-137466. The compound, the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4,223,701, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION), and the like.

Specific examples of the ruthenium compound which is preferably used in the present invention are shown below, but the present invention is not limited thereto.

[化12] [Chemistry 13]

The ruthenium compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. Further, the ruthenium compound is preferably a compound having a high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, measurement by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using a solvent of ethyl acetate at a concentration of 0.01 g/L is preferred.

The present invention can also use a difunctional or trifunctional or higher photopolymerization initiator as a photopolymerization initiator. Specific examples of such a photopolymerization initiator include JP-A-2010-527339, JP-A-2011-524436, WO Publication No. WO2015/004565, and JP-A-2016-532675. The dimer of the oxime compound described in paragraphs 0039 to 0055 of the Japanese Patent Publication No. 0039 to 0055, and the compound (E) and the compound (G) described in JP-A-2013-522445 Cmpd1 to 7 and the like described in International Publication WO2016/034963.

The content of the photopolymerization initiator is preferably from 0.1 to 30% by mass based on the total solid content of the coloring composition. The lower limit is, for example, 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, 20% by mass or less, more preferably 10% by mass or less. The coloring composition may contain only one type of photopolymerization initiator, or may contain two or more types. In the case where two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<<Compound having an epoxy group>> 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 preferred. The upper limit of the epoxy group is preferably 100 or less, more preferably 10 or less, and still more preferably 5 or less.

The epoxy equivalent of the epoxy compound (= the molecular weight of the compound having an epoxy group / the 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 further preferred.

The epoxy compound may be a low molecular compound (for example, having a molecular weight of less than 1,000), or may be a macromolecular compound (for example, a molecular weight of 1,000 or more, and a polymer having a weight average molecular weight of 1,000 or more). The molecular weight of the epoxy compound (in the case of a polymer, a weight average molecular weight) is preferably from 200 to 100,000, more preferably from 500 to 50,000. The upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,500 or less.

For the epoxy compound, paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408 can be used. The compound described in the above. These contents are incorporated in this specification.

In the case where the colored composition of the present invention contains an epoxy compound, the content of the epoxy compound in the total solid content of the colored composition is preferably from 0.1 to 40% by mass. The lower limit is, for example, 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, 30% by mass or less, more 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 at the same time, it is preferable that the total range is the above range.

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

Examples of the organic solvent include the following organic solvents. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and butyrate B. Ester, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (eg, methyl alkoxyacetate, ethyl alkoxylate, butyl alkoxy acetate (eg, methoxy) Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (for example, Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, Propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl ester, ethyl 2-ethoxypropionate), 2-alkoxy-2-methylpropanoate and 2-alkane Ethyl 2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. . Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene. Further, from the viewpoint of improvement in solubility, 3-methoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide are also preferred. The organic solvent may be used singly or in combination of two or more. However, it is preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for reasons such as environmental reasons (for example, it can be 50 mass ppm with respect to the total amount of organic solvents ( The parts per million: parts per million) may be 10 mass ppm or less, or may be 1 mass ppm or less.

The organic solvent may be used singly or in combination of two or more. When two or more organic solvents are used in combination, it is particularly preferred that the above is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol A mixed solution of two or more of an acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

In the present invention, a solvent having a small metal content is preferably used as the solvent. The metal content in the solvent is preferably, for example, 10 parts by mass or less (parts per billion: parts per billion). A solvent having a metal content of a mass ppt (parts per trillion) may be used as needed, for example, supplied by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

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

The solvent may contain isomers (although compounds having the same number of atoms but different structures). Further, the isomer may be contained alone or in combination of plural kinds.

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

The content of the solvent is preferably from 5 to 80% by mass based on the total solid content of the coloring composition. 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, and still more preferably 40% by mass or less.

<<Curing accelerator>> In order to increase the hardness of the pattern or lower the curing temperature, the coloring composition of the present invention may contain a hardening accelerator. Examples of the curing accelerator include a thiol compound and the like.

The thiol compound may, for example, be a polyfunctional thiol compound having two or more fluorenyl groups in the molecule. The polyfunctional thiol compound can be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkane thiol, more preferably a compound having a structure represented by the following formula (T1). Formula (T1) [Chemistry 14] (In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valence.)

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

[化15]

Further, the curing accelerator can also be a methylol-based compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-034963), an amine, a phosphonium salt, a phosphonium salt, or a guanamine. The compound (the above-mentioned, for example, the curing agent described in paragraph 0186 of JP-A-2013-041165), an alkali generating agent (for example, an ionic compound described in JP-A-2014-055114), and an isocyanate compound. (A compound described in Paragraph No. 0071 of JP-A-2012-150180) and an alkoxydecane compound (for example, an alkoxy group having an epoxy group described in JP-A-2011-253054 A decane compound, a sulfonium salt compound (for example, a compound exemplified as an acid generator in paragraph 0216 of JP-A-2015-034963, and a compound described in JP-A-2009-180949).

In the case where the colored composition of the present invention contains a curing accelerator, the content of the curing accelerator in the total solid content of the colored composition is preferably from 0.3 to 8.9% by mass, more preferably from 0.8 to 6.4% by mass.

<<Pigment Derivative>> The coloring composition of the present invention preferably contains a pigment derivative. The pigment derivative may, for example, be a compound having a structure in which a part of a chromophore is substituted with an acid group, a basic group or a quinone imine group.

Examples of the chromophore constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthracene skeleton, and a quinone. Ketone skeleton, Erqijing well skeleton, purple ketone skeleton, lanthanide skeleton, thioindigo skeleton, isoporphyrin skeleton, isoindolinone skeleton, quinoline yellow skeleton, Shilin system a skeleton, a metal complex skeleton, a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a quinoline yellow skeleton, an isoporphyrin skeleton, and a phthalocyanine The skeleton is preferred, and the azo skeleton and the benzimidazolone skeleton are more preferred. As the acid group of the pigment derivative, a sulfo group and a carboxyl group are preferred, and a sulfo group is more preferred. As the basic group which the pigment derivative has, an amine group is preferable, and a tertiary amine is more preferable. Specific examples of the pigment derivative can be referred to, for example, in paragraphs 0162 to 0183 of JP-A-2011-252065, and the contents are incorporated herein by reference.

In the case where the colored composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 30 parts by mass, more preferably from 3 to 20 parts by mass, per 100 parts by mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

<<Interfacial Active Agent>> The colored 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 an anthrone-based surfactant can be used, and coating can be further improved. For reasons of properties, a fluorine-based surfactant is preferred.

When the fluorine-based surfactant is contained in the colored composition of the present invention, the liquid properties at the time of preparing the coating liquid are improved, and the uniformity of the coating thickness can be further improved. In other words, when a film is formed using a coating liquid to which a coloring composition containing a fluorine-based surfactant is applied, the surface tension of the surface of the coating film is lowered, and the uniformity of drying is improved. Therefore, it is possible to further preferably form a film having less uneven coating.

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

Examples of the fluorine-based surfactant include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (all manufactured by DIC Corporation). , Fluorad FC430, FC431, FC171 (above is Sumitomo 3M Limited), Surflon 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 Solutions Inc.) and the like. For the fluorine-based surfactant, the compound described in paragraphs 0015 to 0158 of JP-A-2015-117327, and the compound described in paragraphs 0117 to 0132 of JP-A-2011-132503 can be used.

The fluorine-based surfactant can also preferably be an acrylic compound which has a molecular structure having a functional group containing a fluorine atom, and when a heat is applied, a functional group containing a fluorine atom is cleaved and a fluorine atom is volatilized. As such a fluorine-based surfactant, MEGAFACE DS series (Chemical Industry Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Industry News, February 23, 2016), for example, MEGAFACE can be cited. DS-21.

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

A fluorine-based surfactant can also use a block polymer. For example, the compound described in JP-A-2011-089090 can be mentioned. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound comprising: a repeating unit derived from a (meth) acrylate compound having a fluorine atom; and a source having two or more ( More preferably, it is a repeating unit of a (meth) acrylate compound of an alkoxy group (preferably an ethoxy group, a propenyloxy group) of 5 or more. The following compounds are also exemplified as the fluorine-based surfactant used in the present invention. In the following formula, the % of the ratio of the repeating unit is % by mole. [Chemistry 16] The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000.

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965. As a commercial item, MEGAFACE RS-101, RS-102, RS-718-K, RS-72-K, etc. by DIC Corporation are mentioned, for example.

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

KP-341 (made by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75, No. 90, No. 95 (KYOEISHA CHEMICAL Co., LTD.), W001 is mentioned as a cationic surfactant. (manufactured by Yusho Co., Ltd.) and the like.

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

Examples of the anthrone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co). ., manufactured by Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, KF6002 (above, Shin-Etsu Chemical Co., LTD., BYK307, BYK323, BYK330 (above, BYK-Chemie Corporation) and the like.

In the total solid content of the colored composition, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be used alone or in combination of two or more. In the case where two or more types are included, the total amount is preferably in the above range.

<<Ultraviolet 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 methylbenzimidium compound, a coumarin compound, a salicylic acid compound, a benzophenone compound, a benzotriazole compound, or the like can be used. An acrylonitrile compound, a hydroxyphenyl three-well compound, and the like. For the details, the descriptions of paragraphs 0033 to 0723 of JP-A-2012-208374, and paragraphs 0317 to 0334 of JP-A-2013-068814 can be referred to, and the contents are incorporated herein by reference. Specific examples of the ultraviolet absorber include compounds having the following structures. The commercially available product of the ultraviolet absorber is, for example, UV-503 (manufactured by DAITO CHEMICAL CO., LTD). Further, as the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. can be used. [化17]

In the case where the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, more preferably from 0.1 to 5% by mass. 3% by mass is particularly good. Further, the ultraviolet absorber may be used alone or in combination of two or more. In the case where two or more kinds of ultraviolet absorbers are contained, the total amount thereof is preferably in the above range.

<<Centane coupling agent>> The coloring composition of the present invention can contain a decane coupling agent. In the present invention, the decane coupling agent means a decane compound having a hydrolyzable group and functional groups other than the decane. Further, the hydrolyzable group means a substituent which is directly bonded to a ruthenium atom and which can generate a siloxane chain by a hydrolysis reaction and/or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and a decyloxy group.

The decane coupling agent has at least one selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an amine group, a trimeric isocyanate group, a urea group, a thiol group, a thioether group, and an isocyanate group. The group and the alkoxy decane compound are preferred. Specific examples of the decane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-602). , N-β-aminoethyl-γ-aminopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-603), N-β-aminoethyl-γ-amino group Propyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., LTD., KBE-602), γ-aminopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-903) γ-Aminopropyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., LTD., KBE-903), 3-methacryloxypropyltrimethoxydecane (Shin-Etsu Chemical Co.) Manufactured by, LTD., KBM-503), 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-403), and the like. For the details of the decane coupling agent, the descriptions of paragraphs 0155 to 0158 of JP-A-2013-254047 can be referred to, and the contents are incorporated in the present specification.

In the case where the colored composition of the present invention contains a decane coupling agent, the total solid content of the colored composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, more preferably 0.1 to 0.001% by mass. 5% by mass is particularly good. The colored composition of the present invention may contain only one type of decane coupling agent, or may contain two or more types. In the case where two or more kinds of decane coupling agents are contained, the total amount thereof is preferably in 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-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'. - thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxylamine salts (ammonium salts, primary sulfonium salts, etc.) and the like. In the case where the colored composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the total solid content of the colored composition is preferably 0.01 to 5% by mass. The colored composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. In the case where two or more kinds are contained, the total amount thereof is preferably within the above range.

<<Other Additives>> In the colored composition of the present invention, various additives such as a filler, an adhesion promoter, an antioxidant, an anti-agglomerating agent, and the like can be blended as needed. The additives described in paragraphs 0155 to 0156 of JP-A-2004-295116 can be cited as such additives, and the contents are incorporated in the present specification. In addition, as the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0042 of JP-A-2011-090147), a thioether compound, or the like can be used. As a commercial item, for example, the Adekastab series manufactured by ADEKA CORPORATION (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-) 330, etc.). The antioxidant may be used alone or in combination of two or more. The coloring composition of the present invention can contain the sensitizer, the light stabilizer, and the thermal polymerization described in Paragraph No. 0081 of JP-A-2004-295116, JP-A-2004-295116. Inhibitor.

The content of the Group 2 element (calcium, magnesium, etc.) in the colored composition is preferably 50 ppm by mass, from the viewpoint of suppressing the occurrence of defects or the like, depending on the raw material to be used and the like. Hereinafter, 0.01 to 10 ppm by mass is more preferable. Further, the total amount of the inorganic metal salt in the colored composition is preferably 100 ppm by mass or less, more preferably 0.5 to 50 ppm by mass.

The water content of the colored composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, 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 colored composition of the present invention is preferably from 10 to 25% by mass. The upper limit is preferably 23% by mass or less, 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 of the film surface form (flatness or the like), adjusting the film thickness, and the like. The value of the viscosity can be appropriately selected as needed. For example, it is preferably 0.3 to 50 mPa·s at 25 ° C, more preferably 0.5 to 20 mPa·s. As a method of measuring the viscosity, for example, a viscometer RE85L (rotor: 1°34'×R24, measuring range: 0.6 to 1200 mPa·s) manufactured by TOKI SANGYO CO., LTD. can be used, and the temperature is adjusted to 25 ° C. The measurement is performed in the state.

The coloring composition of the present invention, using a rotary viscometer, the viscosity at 23 ℃ ₂ when measured at a shear rate of 10 s ^-1 at 23 ℃ μ viscosity when measured at a shear rate of 1000 s ^-1 The ratio of μ ₁ , that is, μ ₂ /μ ₁ is preferably 0.75 or more and 1.25 or less. The μ ₂ /μ ₁ system is preferably 0.90 or more, 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 coating property is good, and a film in which thickness unevenness is suppressed can be formed. The method of adjusting μ ₂ /μ _{1 of the} coloring composition within the above range can be adjusted by appropriately adjusting the solid content concentration of the coloring composition, the content of the pigment (DPP), the content of the graft resin A, and the like. Within the scope. For example, in the case where μ ₂ /μ ₁ of the colored composition is to be reduced within the above range, a method of lowering the solid content concentration of the colored composition to the lower limit within the above range is exemplified. Further, in the case where μ ₂ /μ ₁ of the colored composition is to be increased within the above range, a method of increasing the solid content concentration of the colored composition to the upper limit within the above range is mentioned.

The storage container of the coloring composition of the present invention is not particularly limited, and a known storage container can be used. Further, for the purpose of suppressing the incorporation of impurities into the material or the composition, it is preferable to use a multi-layer bottle in which the inner wall of the container is composed of six kinds of six layers of resin or a bottle having a seven-layer structure. As such a container, for example, a container described in JP-A-2015-123351 can be cited.

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

In the case where the coloring composition of the present invention is used as a color filter applied to a liquid crystal display device, the voltage holding ratio of the liquid crystal display element having the color filter is preferably 70% or more, more preferably 90%. the above. A well-known method for obtaining a high voltage holding ratio can be appropriately combined. As a typical method, a material having a high purity (for example, reducing ionic impurities) or an amount of an acidic functional group in the composition can be used. The voltage holding ratio can be measured, for example, by the method described in paragraph 0023 of JP-A-2011-008004, paragraphs 0123 to 0129 of JP-A-2012-224847.

<Method for Preparing Colored Composition> The colored composition of the present invention can be prepared by mixing the above components. When preparing a colored composition, all the components may be simultaneously dissolved and/or dispersed in a solvent to prepare a colored composition, and if necessary, each component may be appropriately used as two or more solutions or dispersions, and when used ( When they are applied, they are mixed to prepare a colored composition.

Further, in the preparation of the colored composition, a process of dispersing the pigment is preferred. In the process of dispersing the pigment, as the mechanical force for dispersing the pigment, compression, pressing, impact, shearing, cavitation, and the like are exemplified. Specific examples of such processes include bead milling, sanding, roll milling, ball milling, paint agitation, microjet, high speed impeller, sand mixing, jet mixing, high pressure wet micronization, ultrasonic dispersion, and the like. Further, in the pulverization of the pigment under sanding (bead milling), it is preferred to carry out the treatment under the following conditions, and the pulverization efficiency is improved by using microbeads having a small diameter and increasing the filling ratio of the microbeads and the like. Further, it is preferred to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. Further, the process for dispersing the pigment and the dispersing machine can be preferably centered on "Dispersion Technology Encyclopedia, Information Systems Co., Ltd., July 15, 2005" or "Centered around Suspension (Solid/Liquid Dispersion System) The process and disperser described in Paragraph No. 0022 of the Japanese Patent Publication No. 2015-157893, issued on October 10, 1978. Further, in the process of dispersing the pigment, the particle may be subjected to a refining treatment by a salt milling step. For example, the materials, the equipment, the processing conditions, and the like used in the salt-grinding step can be referred to, for example, in JP-A-2015-194521 and JP-A-2012-046629.

In the preparation of the colored composition, it is preferred to filter with a filter in order to remove foreign matter or reduce defects and the like. The filter can be used without any particular limitation as long as it is used for a filter or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6 or nylon-6,6), or a polyolefin resin such as polyethylene or polypropylene (PP) may be used. A filter for raw materials such as high density and/or ultra high molecular weight polyolefin resin). Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred.

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

Further, as the filter, a filter using a fibrous filter material is also preferable. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Specific examples of the filter using the fibrous filter material include the SBP type series (SBP008, etc.) manufactured by ROKI TECHNO CO., LTD., the TPR type series (TPR002, TPR005, etc.), and the SHPX type series ( Filter element of SHPX003, etc.).

When using filters, you can combine different filters. In this case, the filtration by each filter may be carried out only once or twice or more. For example, filters of different pore sizes can be combined within the above range. The aperture at this time can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon Mykrolis Corporation), or KITZ MICROFILTER CORPORATION. Further, only the dispersion liquid may be filtered using the first filter, and after mixing other components, the second filter may be used for filtration. As the second filter, a material formed of the same material as the first filter or the like can be used.

<Cured film> The cured film of the present invention is a cured film obtained from the above colored composition of the present invention. The film thickness of the cured film can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

<Pattern Forming Method> Next, a pattern forming method of the present invention will be described. The pattern forming method of the present invention comprises, in order, a step of forming a colored composition layer on a support using the coloring composition of the present invention described above; a step of exposing the colored composition layer into a pattern (exposure step); and developing and removing the coloring A step of forming an unexposed portion of the layer (developing step). Hereinafter, each step will be described.

<<Step of Forming Colored Composition Layer>> In the step of forming the colored composition layer, a colored composition layer is formed on the support using the colored composition.

The support is not particularly limited and can be appropriately selected depending on the use. For example, a glass substrate, a substrate for a solid-state imaging device provided with a solid-state imaging device (light-receiving element) such as a CCD or a CMOS, a germanium substrate, or the like can be given. Further, if necessary, an undercoat layer may be provided on the substrates in order to improve adhesion to the upper layer, prevent diffusion of substances, or achieve planarization of the surface.

The spin coating method, the slit coating method, the inkjet method, and the like are used as a method of applying the coloring composition to the support, and the spin coating method is used for the reason that the effect of the present invention is more remarkably exhibited. Preferably. Further, the coating conditions in the spin coating method differ depending on the solid content concentration of the colored composition, etc., for example, spin coating at a number of revolutions of 300 to 3000 rpm is preferred, and spin coating is performed at a number of revolutions of 800 to 1500 rpm. For better. When it is in this range, it is easy to manufacture the cured film which the thickness unevenness is suppressed.

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

<<Exposure Step>> Next, the colored composition layer is exposed to a pattern (exposure step). For example, by using an exposure apparatus such as a stepper, a mask having a predetermined mask pattern is exposed to the colored composition layer, whereby pattern exposure can be performed. Thereby, the exposed portion can be hardened. As the radiation (light) that can be used at the time of exposure, ultraviolet rays (especially, i-rays) such as g-rays and i-rays are preferably used. The irradiation amount (exposure amount) is 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 can be carried out in a low oxygen atmosphere (for example, 15% by volume, 5% by volume, or substantially oxygen-free) having an oxygen concentration of 19% by volume or less, in addition to being carried out in the atmosphere. Exposure may also be carried out under a high oxygen environment (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. Further, the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m ² to 100000 W/m ² (for example, 5000 W/m ² , 15000 W/m ² , or 35000 W/m ² ). The oxygen concentration and the exposure illuminance can be appropriately combined, and for example, an oxygen concentration of 10% by volume, an illuminance of 10,000 W/m ² , an oxygen concentration of 35 vol%, and an illuminance of 20,000 W/m ² can be used.

<<Developing Step>> Next, the unexposed portion of the colored composition layer was developed and removed to form a pattern. The development removal of the unexposed portion of the colored composition layer can be carried out using a developer. Thereby, the colored composition layer of the unexposed portion in the exposure step is dissolved in the developer, and only the portion which is photohardened remains. As the developer, an organic alkaline developer which does not cause damage to a solid image sensor or a circuit of the substrate is preferable. 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 developing solution may be repeatedly applied every 60 seconds to supply a new developing solution.

As the developer, an alkaline aqueous solution obtained by diluting an alkali agent with pure water is preferably used. Examples of the alkaline agent include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethylhydrogen. Ammonium oxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1 , an organic basic compound such as 8-diazabicyclo[5.4.0]-7-undecene, or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, etc. Inorganic basic compound. 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, a surfactant may be contained in the developer. Examples of the surfactant include the above surfactants, and nonionic surfactants are preferred. The developer can be temporarily produced into a concentrate from the viewpoint of convenient transfer or storage, and diluted to a desired concentration at the time of use. The dilution ratio is not particularly limited, and can be set, for example, in the range of 1.5 to 100 times. Further, when a developer containing such an alkaline aqueous solution is used, it is preferred to wash (rinse) with pure water after development. Further, when a developer containing such an alkaline aqueous solution is used, it is preferred to wash (rinse) with pure water after development.

After the development, it is preferred to carry out heat treatment (post-baking) after drying. The post-baking is heat treatment after development for completely curing, and the heating temperature is preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Further, in the case where the support for forming the cured film includes an organic electroluminescence (organic EL) element or an image sensor having a photoelectric conversion film made of an organic material, the post-baking temperature is preferably 150 ° C or lower. The lower limit can be, for example, 50 ° C or higher. The film (cured film) after development can be post-baked in a continuous or intermittent manner by using a heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating machine as the above conditions. In addition, the pattern forming method may further include a process based on dry etching. For the dry etching process, for example, the dry etching process described in paragraphs 0137 to 0165 of the publication WO2018/061781 can be cited.

It is preferred that the cured film has high flatness. Specifically, the surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, still more preferably 15 nm or less. The lower limit is not specified, and is preferably 0.1 nm or more. Regarding the measurement of the surface roughness, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco Co., Ltd. can be used for measurement. Further, the contact angle of water on the cured film can be set to a suitably preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured by, for example, a contact angle meter CV-DT・A type (manufactured by Kyowa Interface Science Co., LTD.).

Ideally, each pattern (pixel) has a high volume resistance value. Specifically, the volume resistivity of the pixel is preferably 10 ⁹ Ω·cm or more, and more preferably 10 ¹¹ Ω·cm or more. The upper limit is not specified, but is preferably, for example, 10 ¹⁴ Ω·cm or less. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

<Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention has the above-described 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 depending on the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. The color filter of the present invention can be used for a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Film Semiconductor), an image display device, or the like.

<Solid-State Imaging Device> The solid-state imaging device of the present invention has the cured film of the present invention described above. The configuration of the solid-state image sensor of the present invention is not particularly limited as long as it has a cured film of the present invention and functions as a solid-state image sensor, and the following structures are exemplified.

The imaging element has a structure in which a plurality of photo-electric regions including light-receiving regions constituting a solid-state imaging device (CCD (Charge Coupled Device) image sensor, CMOS (Complementary Metal Oxide Film Semiconductor) image sensor, etc.) are provided on the substrate. A transmission electrode composed of a polar body and a polycrystalline silicon has a light-shielding film having only a light-receiving portion of the photodiode that is opened on the photodiode and the transfer electrode, and has a light-shielding film covering the entire surface of the light-shielding film and receiving light of the photodiode A device protective film made of tantalum nitride or the like formed by a portion, and has a color filter on the device protective film. Further, it may be a structure having a light collecting means (for example, a microlens or the like, the same below) on the underside of the color filter (on the side close to the substrate) on the device protective film or a light collecting means on the color filter. Structure and so on. Further, the color filter may have, for example, a structure in which a cured film forming each colored pixel is embedded in a space partitioned by a partition wall. In this case, the partition wall has a low refractive index with respect to each of the colored pixel elements. An example of the image pickup apparatus having such a configuration is the apparatus described in Japanese Laid-Open Patent Publication No. 2012-227478, and the Japanese Patent Publication No. JP-A-2014-179577. The imaging device including the solid-state imaging device of the present invention can be used as an in-vehicle camera or a surveillance camera in addition to a digital camera or an electronic device having an imaging function (a mobile phone or the like).

<Image Display Device> The cured film of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. The definition of the image display device or the details of each image display device is described, for example, in "Electronic display device (Kogyo Chosakai Publishing Co., Ltd., issued in 1990)", "Display device (Ibukishun) Zhang, Sangyo Tosho Publishing Co., Ltd., issued in 1989)" and so on. Further, the liquid crystal display device is described, for example, in "Next Generation Liquid Crystal Display Technology (Edited by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the "next-generation liquid crystal display technology" described above. [Examples]

Hereinafter, the present invention will be further specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, “parts” and “%” are quality standards unless otherwise specified.

<Preparation of Colored Composition> [Preparation of Colored Composition] A colored composition was prepared by stirring and mixing the raw materials shown below. Further, as the dispersion, a dispersion prepared in the following manner was used. Further, the numerical values described in the column of PGMEA in the following table are values including the PGMEA contained in the dispersion. Further, the numerical values described in the following tables are parts by mass.

(Preparation of a dispersion liquid) The pigment, the pigment derivative, and the resin of the type described in the column of the dispersion liquid of the following table are mixed in the mass part of the dispersion liquid of the following table, and the propylene glycol as a solvent is further added. A mixture of monomethyl ether acetate (PGMEA) was prepared. 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added to the mixed solution, and dispersion treatment was carried out for 5 hours using a paint shaker, and the beads were separated by filtration to prepare a dispersion having a solid concentration of 18% by mass.

[Table 4]

The raw materials described in the above table are as follows. In addition, the "content of the graft resin A" in the above table is a value of the content (% by mass) of the graft resin (graft resin A) in the total mass of the resin contained in the coloring composition, and the graft resin (Graft resin A) contains 20 mol% or more of repeating unit A of a graft chain having a poly(meth)acrylate structure as a main chain and a polyester structure in a side chain.

(Pigment) PR254: CI Pigment Red 254 (pigment represented by formula (DPP)) PR255: CI Pigment Red 255 (pigment represented by formula (DPP)) PR272: CI Pigment Red 272 (pigment represented by formula (DPP)) PO71: CI Pigment Orange 71 (pigment represented by formula (DPP)) PO73: CI Pigment Orange 73 (pigment represented by formula (DPP)) PY139: CI Pigment Yellow 139 (except pigment represented by formula (DPP)) Pigment)

(Pigment Derivative) B-1: Compound of the following structure [Chem. 18]

(Resin) C-1: Resin of the following structure (Mw = 20000, the value noted in the main chain is the molar ratio of the repeating unit, and the value on the side chain is the number of repeating units. C-1 is The above grafted resin A.) C-2: a resin having the following structure (Mw = 24000, the value noted in the main chain is the molar ratio of the repeating unit, and the value on the side chain is the number of repeating units. C-2 is the above-mentioned graft resin A.) C-3: a resin having the following structure (Mw = 11,000, the value noted in the main chain is the molar ratio of the repeating unit.) C-4: Resin of the following structure (Mw=22900, the value of the note on the main chain is the molar ratio of the repeating unit.) [Chem. 19]

(alkali soluble resin) D-1: the above resin C-3

(Polymerizable compound) E-1: NK ESTER A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) E-2: ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.) E-3: NK ESTER A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

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

(Surfactant) G-1: The following compound (Mw = 14000). In the following formula, the % of the ratio of the repeating unit is % by mole. [Chemistry 20]

(Ultraviolet absorber) H-1: UV-503 (manufactured by DAITO CHEMICAL CO., LTD.)

<Evaluation> (Measurement of viscosity ratio μ ₂ /μ ₁ ) About the coloring composition which was just prepared, using a rotational viscometer (MCR301, manufactured by Anton Paar), 23 measured at a shear rate of 1000 s ^-1 was measured. The viscosity μ ₂ at ° C is proportional to the viscosity μ ₁ at 23 ° C (μ ₂ /μ ₁ ) measured at a shear rate of 10 s ^-1 .

(Evaluation of thickness unevenness) On a 8 inch (20.32 cm) tantalum wafer, the composition was colored by spin coating with a spin coater (rotation speed = 0050 rpm) so that the film thickness after prebaking was 0.64 μm. Next, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 °C. Then, a cured film was further formed by heating at 200 ° C for 300 seconds using a hot plate. With respect to the film thickness of the obtained cured film, an optical film thickness meter (F50, manufactured by Filmetrics Japan, Inc.) was used to measure 13 at equal intervals in the outer-center-outer circumferential direction (diameter direction) of the 8-inch wafer. The difference between the maximum value and the minimum value (Δt) of the film thickness was obtained from the film thickness at the point. Thickness unevenness was evaluated using the value of Δt. The smaller Δt, the smaller the thickness unevenness.

[table 5]

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

Claims (14)

A colored composition comprising a pigment represented by the formula (DPP), a resin, a photopolymerization initiator, and a polymerizable compound, the resin comprising a graft resin comprising 20 mol% or more of poly(A) a repeating unit A having a acrylate structure as a main chain and having a graft chain of a polyester structure in a side chain, and 60% by mass or more of the resin contained in the coloring composition is the graft resin; Formula (DPP) Wherein R ¹ and R ² each independently represent 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, and m1 and m2 each independently represent an integer of 0 to 5, and when m1 is 2 or more, m1 R ^{1 's} may be the same, Alternatively, in the case where m2 is 2 or more, m2 R ^{2 's} may be the same or different. The colored composition according to claim 1, wherein the pigment represented by the formula (DPP) is selected from the group consisting of color index pigment red 254, color index pigment red 255, color index pigment red 272, colorimetric color. At least one of the index pigment orange 71 and the colorimetric index pigment orange 73. The colored composition according to claim 1, wherein the graft chain is a structure represented by the formula (G-1), the formula (G-2) or the formula (G-3); R ^G1 represents an alkylene group, W ¹⁰⁰ represents a hydrogen atom or a substituent, and n1 to n3 each independently represent an integer of 3 or more. The colored composition according to any one of claims 1 to 3, wherein the graft chain comprises a polyester structure derived from a compound selected from the group consisting of ε-caprolactone and δ-valerolactone . The coloring composition according to any one of claims 1 to 3, wherein the repeating unit A has a weight average molecular weight of 1,000 or more. The colored composition according to any one of claims 1 to 3, wherein the polymerizable compound contains a polymerizable compound having an acid group. The coloring composition according to any one of the first to third aspects of the present invention, wherein the content of the polymerizable compound is 100 parts by mass or less based on 100 parts by mass of the graft resin. The coloring composition according to any one of the items 1 to 3, wherein the content of the graft resin is 30 to 90% by mass based on 100 parts by mass of the pigment represented by the formula (DPP). Share. The colored composition according to any one of claims 1 to 3, wherein a viscosity μ ₂ at 23 ° C and a shear at a shear rate of 1000 s ^-1 are used using a rotational viscometer. The ratio of the viscosity μ ₁ at 23 ° C measured at a cutting speed of 10 s ^-1 , that is, μ ₂ /μ ₁ is 0.75 or more and 1.25 or less. A cured film obtained by hardening a colored composition according to any one of claims 1 to 9. A pattern forming method comprising: a step of forming a colored composition layer on a support by using the colored composition according to any one of claims 1 to 9; exposing the colored composition layer a step of patterning; and a step of developing and removing the unexposed portion of the colored composition layer. A color filter comprising the cured film according to claim 10 of the patent application. A solid-state image sensor having a cured film as described in claim 10 of the patent application. An image display device having the cured film as described in claim 10 of the patent application.