WO2019058859A1

WO2019058859A1 - Colored composition, cured film, pattern formation method, color filter, solid imaging element, and image display device

Info

Publication number: WO2019058859A1
Application number: PCT/JP2018/031053
Authority: WO
Inventors: 裕樹奈良
Original assignee: 富士フイルム株式会社
Priority date: 2017-09-20
Filing date: 2018-08-22
Publication date: 2019-03-28
Also published as: JP7090628B2; JPWO2019058859A1; TW201915099A

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

Colored composition, cured film, pattern forming method, color filter, solid-state imaging device 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 imaging device, and an image display device.

2. Description of the Related Art In recent years, with the widespread use of digital cameras, mobile phones with cameras, etc., the demand for solid-state imaging devices such as charge coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements. The color filter usually has pixels (colored patterns) of three primary colors of red, green and blue, and plays a role of separating transmitted light into the three primary colors.

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

JP, 2009-96977, A JP, 2011-153280, A Unexamined-Japanese-Patent No. 2010-217872

However, the coloring composition containing the diketopyrrolopyrrole pigment can not be said to have sufficient coatability, and tends to cause thickness unevenness.

Therefore, an object of the present invention is to provide a coloring composition which has good coatability and can produce a film with suppressed thickness unevenness. Another object of the present invention is to provide a cured film, a pattern forming method, a color filter, a solid-state imaging device, and an image display device.

As a result of intensive investigations, the inventor of the present invention has found that the coloring composition to be described later has good coatability and can produce a film with suppressed thickness unevenness, and has completed the present invention. That is, the present invention is as follows.
It is a coloring composition containing the pigment represented by <1> Formula (DPP), resin, a photoinitiator, and a polymeric compound,
The resin includes a graft resin having a poly (meth) acrylate structure as a main chain and containing 20 mol% or more of a repeating unit A having a graft chain of a polyester structure in a side chain,
A coloring composition in which 60% by mass or more of the resin contained in the coloring composition is a graft resin;
Formula (DPP)

In the formula, R ¹ and R ² are each independently 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 Represents
R ^D1 and R ^D2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
m1 and m2 each independently represent an integer of 0 to 5,
When m1 is 2 or more, the m1 R ^{1 s} may be identical to or different from each other,
If m2 is 2 or more, may be respectively m2 one of R ² identical or different.
The pigment represented by <2> Formula (DPP) is at least one selected from color index pigment red 254, color index pigment red 255, color index pigment red 272, color index pigment orange 71, and color index pigment orange 73 The coloring composition as described in <1> which is a seed | species.
<3> The colored composition according to <1> or <2>, which is a structure represented by Formula (G-1), Formula (G-2), or Formula (G-3):

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 coloring composition according to any one of <1> to <3>, wherein the graft chain comprises a polyester structure derived from a compound selected from ε-caprolactone and δ-valerolactone.
<5> The coloring composition according to any one of <1> to <4>, wherein the weight average molecular weight of the repeating unit A is 1,000 or more.
<6> The colored composition according to any one of <1> to <5>, wherein the polymerizable compound comprises a polymerizable compound having an acid group.
<7> The colored composition according to any one of <1> to <6>, wherein the content of the polymerizable compound is 100 parts by mass or less with respect to 100 parts by mass of the graft resin.
The coloring composition in any one of <1>-<7> whose content of <8> graft resin is 30-90 mass parts with respect to 100 mass parts of a pigment represented by Formula (DPP) .
<9> Ratio of viscosity μ ₂ at 23 ° C. measured at a shear rate of 1000 s ⁻¹ to viscosity μ ₁ at 23 ° C. measured at a shear rate of 10 s ⁻¹ using a rotational viscometer The coloring composition according to any one of <1> to <8>, wherein μ ₂ / μ ₁ is 0.75 or more and 1.25 or less.
<10> A cured film obtained by curing the colored composition according to any one of <1> to <9>.
<11> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <9>,
Exposing the colored composition layer in a pattern;
Developing and removing the unexposed area of the colored composition layer;
A pattern forming method including:
The color filter containing the cured film as described in <12><10>.
The solid-state image sensor which has a cured film as described in <13><10>.
The image display apparatus which has a cured film as described in <14><10>.

According to the present invention, it is possible to provide a colored composition which has good coatability and can produce a film having suppressed thickness unevenness. Moreover, a cured film, a pattern formation method, a color filter, a solid-state imaging device, and an image display apparatus can be provided.

Hereinafter, the contents of the present invention will be described in detail.
In the notation of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, as light used for exposure, generally, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), actinic rays such as X-rays, electron beams and the like can be mentioned.
In the present specification, a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit value and the upper limit value.
As used herein, total solids refers to the total mass of all components of the composition excluding the solvent.
In the present specification, infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
In the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acryl” represents both or either of acrylic and methacryl, “(meth) acrylate” ) Allyl "represents both or any of allyl and methallyl, and" (meth) acryloyl "represents both or any of acryloyl and methacryloyl.
In the present specification, the term "process" is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process. .
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).
In the present specification, a pigment means an insoluble dye compound which is hardly soluble in a solvent. The pigment used in the present invention preferably has, for example, an amount dissolved in 100 g of propylene glycol monomethyl ether acetate at 25 ° C. and an amount dissolved in 100 g of water at 25 ° C. The content is more preferably 05 g or less, further preferably 0.01 g or less.

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

According to the study of the present inventors, diketopyrrolopyrrole pigments tend to have relatively high interactions between the pigments, and the coloring composition containing diketopyrrolopyrrole pigments has a viscosity which increases as the shear rate increases. It has been found that the drop is large and the change in viscosity with respect to the shear rate tends to be large. Since the coloring composition containing the diketopyrrolopyrrole pigment has such viscosity characteristics, it was presumed that thickness unevenness would easily occur. For example, in the case where a coloring composition containing a diketopyrrolopyrrole pigment is spin-coated, the centrifugal force becomes stronger as it moves away from the rotation center, so the film thickness near the rotation center becomes thicker than the film thickness of the outer periphery. It is presumed that the thickness is easily made uneven as a result.
According to the coloring composition of the present invention, the pigment represented by the formula (DPP) described later (hereinafter also referred to as a pigment (DPP)) and the graft resin containing 20 mol% or more of the specific repeating unit A described above Since the resin containing a mass% or more is included, the interaction between the pigments (DPP) in the coloring composition is small, and the dispersibility of the pigment (DPP) is good. Therefore, the change in viscosity with respect to the shear rate is small. As a result, it is presumed that a film having good coatability and suppressed thickness unevenness could be produced. For this reason, the coloring composition of the present invention has good coatability, and can produce a film in which thickness unevenness is suppressed.

As the coloring composition, as a pigment (DPP), at least one selected from color index pigment red 254, color index pigment red 255, color index pigment red 272, color index pigment orange 71, and color index pigment orange 73 is used In such a case, the improvement effect of thickness unevenness is remarkably exhibited, and when color index pigment red 254 is used as the pigment (DPP), the improvement effect of thickness unevenness is more significantly exhibited.

Hereinafter, each component used for the coloring composition of this invention is demonstrated.

<< pigment represented by formula (DPP) >>
The coloring composition of the present invention contains a pigment represented by the formula (DPP). This pigment is a pigment having a diketopyrrolopyrrole skeleton. Hereinafter, the pigment represented by the formula (DPP) is also referred to as a pigment (DPP).
Formula (DPP)

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

The halogen atom represented by R ¹ and R ^2, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.

The carbon number of the alkyl group represented by R ¹ , R ² , R ^D1 and R ^D2 is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 8. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent. As a substituent, the group mentioned by the substituent T mentioned later is mentioned.

^6-30 are preferable, as for carbon number of the aryl group which ^RD1 and ^RD2 represent, 6-20 are more preferable, and 6-12 are still more preferable. The aryl group may have a substituent. As a substituent, the group mentioned by the substituent T mentioned later is mentioned.
The heteroaryl group represented by R ^D1 and R ^D2 may be a single ring or a fused ring. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group is preferably a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The heteroaryl group may have a substituent. As a substituent, the group mentioned by the substituent T mentioned later is mentioned.

R ¹ and R ² are preferably each independently a halogen atom, an alkyl group or a cyano group, more preferably a halogen atom or an alkyl group, and still more preferably a halogen atom.

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

As the substituent T, the following groups may be mentioned. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably An aryl group having 6 to 30 carbon atoms, an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably 6 to carbon atoms 30) aryloxy group), heteroaryloxy group, acyl group (preferably having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably having 2 to 30 carbon atoms) Is an aryloxycarbonyl group having 7 to 30 carbon atoms, a heteroaryloxycarbonyl group, an acyloxy group Preferably, it is an acyloxy group having 2 to 30 carbon atoms, an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonyl Amino group (preferably aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (Preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably having a carbon number of 1 to 30), an alkylsulfonyl group (preferably having a carbon number 1 to 30), an arylsulfonyl group (preferably charcoal) 6 to 30), heteroarylsulfonyl (preferably having a carbon number of 1 to 30), alkylsulfinyl (preferably having a carbon number of 1 to 30), arylsulfinyl (preferably having a carbon number of 6 to 30), heteroarylsulfinyl group (Preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxy group, carboxyl group, sulfo group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imidic acid group, mercapto Group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, hydrazino group, imino group, heteroaryl group (preferably having a carbon number of 1 to 30). When these groups are further substitutable groups, they may further have a substituent. As a substituent, the group demonstrated by the substituent T mentioned above is mentioned.

The compound of the following structure is mentioned as a specific example of a pigment (DPP). In the following table, when the designation of the substituent is "-", it indicates that it is a hydrogen atom. For example, DPP-1 is a compound in which Z ¹ and Z ³ to Z ¹⁰ are hydrogen atoms, and Z ² is -OCH ₃ . Also, Me represents a methyl group, and Ph represents a phenyl group.

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

In the present invention, as the pigment (DPP), color index (CI) pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 272, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73 is preferable, and C.I. I. Pigment red 254 is more preferred.

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

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

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

C. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 35, 53, 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, 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 like (or more, and yellow pigment),
C. I. Pigment orange 2, 5, 13, 16, 17: 1, 13, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 etc. (above, orange Color pigment),
C. I. Pigment red 1,2,3,4,5,6,7,9,10,14,17,22,23,33,41,48: 1,48: 2,48: 3,48: 4, 49, 49: 1, 49: 2, 25: 2, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 242, 242, 246, 264, 269, 270, 279, etc. (above, red pigment),
C. I. Pigment green 7, 10, 36, 37, 58, 59 (above, green pigment),
C. I. Pigment violet 1,19,23,27,32,37,42 etc (above, purple pigment),
C. I. Pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 60, 64, 66, 79, 80 (the above, blue pigment).

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

The dye is not particularly limited, and known dyes can be used. The chemical structure includes pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes can be used. Further, a thiazole compound described in JP-A-2012-158649, an azo compound described in JP-A-2011-184493, and an azo compound described in JP-A-2011-145540 can also be preferably used. Further, as the yellow dye, a quinophthalone compound described in paragraph 0011 to 0034 of JP-A-2013-54339, a quinophthalone compound described in paragraph 0013 to 0058 of JP-A 2014-26228, or the like can be used.

Moreover, a pigment | dye multimer can also be used as another coloring agent. The dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is particles, it is usually dispersed in a solvent. Used. The dye multimer in a particulate state can be obtained, for example, by emulsion polymerization, and the compounds and production methods described in JP-A-2015-214682 can be mentioned as specific examples. The dye multimer has two or more dye structures in one molecule, and preferably three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. Plural dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and still more preferably 6000 or more. The upper limit is more preferably 30000 or less, further preferably 20000 or less. As the dye multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742 and the like can also be used.

The other colorant is preferably a yellow colorant, more preferably a yellow pigment, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. Pigment yellow 185 or more preferably one or more selected from C.I. I. Pigment yellow 139 and C.I. I. Pigment yellow 185 or more preferably one or more selected from C.I. I. Pigment Yellow 139 is particularly preferable. According to this aspect, it is easy to obtain better coatability. Furthermore, spectral characteristics preferable for color reproducibility can be obtained.

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

<< Resin >>
The coloring composition of the present invention contains a resin. In the present invention, the resin is an organic compound other than the colorant and is an organic compound having a molecular weight of 2,000 or more. The resin is blended, for example, in applications of dispersing particles such as pigments in a composition and applications of a binder. In addition, resin used mainly for disperse | distributing particle | grains, such as a pigment, is also called a dispersing agent. However, such an application of the resin is an example, and can be used for purposes other than such an application.

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. 3,000 or more are preferable and, as for a minimum, 5,000 or more are more preferable.

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

The above-mentioned repeating unit A in the graft resin A is a repeating unit having a poly (meth) acrylate structure as a main chain and having a polyester chain as 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, but the longer the graft chain, the higher the steric repulsion effect, and the dispersibility of the pigment (DPP) can be enhanced. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and 60 to 60 atoms excluding hydrogen atoms. More preferably, it is 500.

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

Examples of the graft chain include structures represented by Formula (G-1), Formula (G-2) or Formula (G-3).

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

Each of n1 to n3 independently represents an integer of 3 or more, preferably 4 or more, and more preferably 5 or more. For example, 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. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, from the viewpoint of improving the dispersibility of the pigment (DPP), a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable. The alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.

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

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

In the formula, 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 carbon number of the alkyl group represented by R ^A1 is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. R ^A1 is preferably a hydrogen atom or a methyl group.

^Examples of the divalent linking group represented by L ^A1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, And -SO _2- , -CO-, -O-, -COO-, OCO-, -S- and a group formed by combining two or more of these. The alkylene group may be linear, branched or cyclic, and is preferably linear or branched.

W ^A1 represents a graft chain of polyester structure. The graft chain of the polyester structure includes the above-mentioned graft chain, and is preferably a graft chain having a structure represented by 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 10000, and still more preferably 1000 to 7500. In the present invention, the weight average molecular weight of the repeating unit A is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the same repeating unit. For example, repeating unit A can be formed by polymerizing a macromonomer. Here, the macromonomer means a polymer compound in which a polymerizable group is introduced at the polymer end. When the repeating unit A is formed using the macromonomer, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the repeating unit A.

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

The graft resin A used in the present invention may further contain a repeating unit other than the above-mentioned repeating unit A. As another repeating unit, the repeating unit which has an acidic radical, the repeating unit which has a polymeric group, etc. are mentioned. Examples of the acid group include a carboxyl group, a sulfo group and a phosphate group. Examples of the polymerizable group include ethylenic unsaturated groups such as vinyl group, (meth) allyl group and (meth) acryloyl group.

By the graft resin A further including a repeating unit having an acid group, an effect of imparting alkali developability and improving resolution can be expected. Moreover, since the graft resin A further contains the repeating unit which has a polymeric group, the cured film excellent in various physical properties, such as heat resistance, is easy to be obtained.

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

As a specific example of graft resin A, resin of the following structure is mentioned. The graft resin A can be referred to the description of paragraph Nos. 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

(Other resin)
The coloring composition of the present invention can further contain a resin other than the graft resin A described above (hereinafter, also referred to as another resin). As other resin, resin (linear organic high molecular polymer) etc. which do not have a graft chain are mentioned, for example. An alkali-soluble resin etc. are mentioned as an example of another resin.

The alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali dissolution. As a group which promotes alkali dissolution (hereinafter, also referred to as an acid group), for example, a carboxyl group, a phosphate group, a sulfo group, a phenolic hydroxy group and the like can be mentioned, with a carboxyl group being preferable. The type of the acid group possessed by the alkali-soluble resin may be only one type, or two or more types.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 100,000. The number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.

From the viewpoint of heat resistance, the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin. Further, from the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

The alkali-soluble resin is preferably a polymer having a carboxyl group in a side chain. For example, a copolymer having a repeating unit derived from a monomer such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinylbenzoic acid, partially esterified maleic acid, Examples thereof include alkali-soluble phenol resins such as novolac resins, acid cellulose derivatives having a carboxyl group in a side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Can be mentioned. Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like. Other monomers include N-substituted maleimide monomers such as N-phenyl maleimide and N-cyclohexyl maleimide. These other monomers copolymerizable with (meth) acrylic acid may be only one type or two or more types.

As an alkali soluble resin, benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate A multicomponent copolymer composed of / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate with another monomer, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / described in JP-A-7-140654. Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used. Further, as a commercial product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can also be used.

The alkali-soluble resin can also be an alkali-soluble resin having a polymerizable group. Examples of the polymerizable group include (meth) allyl group and (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in a side chain is useful. Commercial products of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264. KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (both manufactured by Daicel Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UBC 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 comprises at least one compound selected from a compound represented by the following formula (ED1) and a compound represented by formula (1) in JP-A-2010-168539 (hereinafter referred to as “ether dimer It is also preferable to include a polymer formed by polymerizing a monomer component including “sometimes referred to as

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

Specific examples of the ether dimer include, for example, the compounds described in Paragraph No. 0317 of JP-A-2013-29760, the contents of which are incorporated herein. The ether dimer may be only one type, or two or more types.

As a polymer formed by polymerizing a monomer component containing an ether dimer, for example, a polymer of the following structure can be mentioned.

The alkali-soluble resin may contain a repeating unit derived from a compound represented by the following formula (X).

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

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

The alkali-soluble resin can be referred to the description in paragraphs 0558 to 0571 of JP 2012-208494 A (paragraph 0685 to 0700 in the corresponding US Patent Application Publication 2012/0235099), the contents of which are incorporated herein by reference. Incorporated into the book. In addition, the copolymer (B) described in paragraphs 0029 to 0063 of JP 2012-32767 A and the alkali-soluble resin used in the examples, paragraph 0088 to 0098 of JP 2012-208474 A. Binder resin described and binder resin used in Examples, Binder resin described in paragraphs 0022 to 0032 of JP 2012-137531 A and binder resin used in Examples, JP 2013-024934 Binder resins described in paragraphs 0132 to 0143 of the gazette and binder resins used in the examples, binder resins used in paragraphs 0092 to 0098 of JP 2011-242752 A and examples, JP 2012 Paragraph No. 0030 of Japanese Patent Application Publication No. 032770 0072 can also be used a binder resin according to. The contents of these are incorporated herein.

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

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

<< polymeric compound >>
The coloring composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated group. As an ethylenically unsaturated group, a vinyl group, a (meth) allyl group, a (meth) acryloyl group etc. are mentioned. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

The polymerizable compound may be in any of chemical forms such as monomers, prepolymers and oligomers, but monomers are preferred. The molecular weight of the polymerizable compound is preferably less than 2000, and more preferably 1,500 or less. The lower limit is more preferably 150 or more, and still more preferably 250 or more.

The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and 3 to 6 ethylenically unsaturated groups. More preferably, it is a compound containing one. 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 are described in paragraph Nos. 0095 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraph 0254-0257 of JP2008-292970A. Compounds are included, the contents of which are incorporated herein.

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., Ltd.) Made, Dipentaerythritol penta (meth) acrylate (Commercial product: KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (Commercial product: KAYARAD DPHA; Nippon Kayaku ( Ltd. product, NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd. product, and the compound of the structure where these (meth) acryloyl groups are linked via ethylene glycol and / or propylene glycol residue (For example, commercially available from Sartmar , SR454, SR499) is preferable. These oligomer types can also be used. In addition, 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 as the polymerizable compound. Moreover, as a polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available products of trifunctional (meth) acrylate compounds include Alonics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.

The polymerizable compound may have an acid group. By using the polymerizable compound having an acid group, the colored composition layer in the unexposed area is easily removed at the time of development, and the generation of development residues can be effectively suppressed. As an acid group, a carboxyl group, a sulfo group, a phosphoric acid group etc. are mentioned, A carboxyl group is preferable. Commercially available products of the radically polymerizable compound having an acid group include Alonics M-510 and M-520, and Alonics TO-2349 (manufactured by Toagosei Co., Ltd.).

The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g. When the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the solubility in a developer is good, and more excellent developability can be obtained. If the acid value of the polymerizable compound is 40 mg KOH / g or less, it is advantageous in terms of production and handling.

As a polymerizable compound, a compound having a caprolactone structure is also a preferable embodiment. Examples of the polymerizable compound having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

The compound which has an alkylene oxy group can also be used for a polymeric compound. The polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups. More preferably, it is a 3- to 6-functional (meth) acrylate compound. As a commercial item of a polymerizable compound having an alkyleneoxy group, for example, SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, a trifunctional (meth) having three isobutylene oxy groups Examples thereof include KAYARAD TPA-330 which is an acrylate.

As polymerizable compounds, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, The urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, it is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. As commercial products, UA-7200 (Shin-Nakamura Chemical Co., Ltd. product), DPHA-40H (Nippon Kayaku Co., Ltd. product), UA-306H, UA-306T, UA-306I, AH-600, T- 600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
As the polymerizable compound, it is also preferable to use 8UH-1006, 8UH-1012 (above, Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.), or the like.
Further, as the polymerizable compound, compounds described in JP-A-2017-48367, JP-A-5605891 and JP-A-6031807 can also be used.

The content of the polymerizable compound is preferably 0.1 to 50% by mass in the total solid content of the coloring composition. As for a minimum, 0.5 mass% or more is more preferable, and 1 mass% or more is still more preferable. The upper limit is more preferably 45% by mass or less, and still 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 60 parts by mass or less with respect to 100 parts by mass of the graft resin A described above. Is more preferred. When the content of the polymerizable compound is in the above range, the dispersion of the pigment (DPP) in the composition is stable, and further, excellent developability can be obtained.
The polymerizable compounds may be used alone or in combination of two or more. When two or more polymerizable compounds are used in combination, the total of them is preferably in the above range.

<< photoinitiator >>
The coloring composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization reaction of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet to visible region are preferred. In addition, it may be a compound which produces an active radical by causing an action with a photoexcited sensitizer.

As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound, a hexaarylbiimidazole, an oxime compound, an organic peroxide, Thio compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds and the like can be mentioned. The photopolymerization initiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole from the viewpoint of exposure sensitivity. Dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds are preferred, and oxime compounds, α-hydroxy ketone compounds, α-hydroxy ketone compounds More preferred are compounds selected from amino ketone compounds and acyl phosphine compounds, and more preferred are oxime compounds. With regard to the photopolymerization initiator, the description of paragraph Nos. 0065 to 0111 of JP-A-2014-130173 and paragraph Nos. 0274 to 0306 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification. .

Examples of commercially available α-hydroxy ketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (manufactured by BASF Corporation) and the like. Examples of commercially available α-amino ketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF Corporation). Examples of commercially available products of acyl phosphine compounds include IRGACURE-819, DAROCUR-TPO (all manufactured by BASF Corp.) and the like.

Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, the compounds described in JP-A-2006-342166, and the like. C. S. Perkin II (1979, pp. 1653-1660), a compound described in J. Am. C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), a compound described in JP-A-2000-66385, Compounds described in JP-A-2000-80068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-19766, Patent No. Examples thereof include the compounds described in 6065596, the compounds described in International Publication WO 2015/152153, and the compounds described in International Publication WO 2017/051680. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- On, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy Examples include carbonyloxyimino-1-phenylpropan-1-one and the like. As commercially available products of oxime compounds, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03 and IRGACURE-OXE04 (all manufactured by BASF Corporation) are also suitably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (made by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), Adeka ARKules NCI-930 And Adeka Optomer N-1919 (photopolymerization initiator 2 of JP 2012-14052 A) (all manufactured by ADEKA Co., Ltd.).

Further, as oxime compounds other than those described above, compounds described in JP-T-2009-519904, in which an oxime is linked to the N-position of a carbazole ring, and compounds described in US Pat. No. 7,626,957, in which a hetero substituent is introduced in the benzophenone moiety And compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site, a ketoxime compound described in WO2009 / 131189, the same triazine skeleton and oxime skeleton. The compound described in US Pat. No. 7,556,910, which is contained in the molecule, and the compound described in JP2009-221114A, which has a maximum absorption wavelength at 405 nm and has a good sensitivity to a g-line light source It is also good.

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. As specific examples of the oxime compound having a fluorene ring, compounds described in JP-A-2014-137466 can be mentioned. This content is incorporated herein.

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

In the present invention, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used as a photopolymerization initiator. As a specific example of such an oxime compound, the compound described in International Publication WO 2013/083505 can be mentioned.

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

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. As specific examples of the oxime compound having a nitro group, compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and patent 4223071 Compounds described in Paragraph Nos. 0007 to 0025 of the gazette, Adeka Arkles NCI-831 (manufactured by ADEKA Co., Ltd.), and the like.

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

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

In the present invention, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator. As specific examples of such a photopolymerization initiator, paragraph Nos. 0417 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication WO2015 / 004565, JP-A-2016-532675. , A dimer of the oxime compound described in paragraph Nos. 0039 to 0055 of International Publication WO 2017/033680, a compound (E) and a compound (G) described in JP-A-2013-522445, an international Examples thereof include Cmpd 1 to 7 described in published WO 2016/034963.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass in the total solid content of the coloring composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 20% by mass or less and still 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. When 2 or more types of photoinitiators are included, it is preferable that the total amount of them becomes said 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 preferable. 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 (= molecular weight of compound having an epoxy group / number of epoxy groups) is preferably 500 g / eq or less, more preferably 100 to 400 g / eq, and 100 to 300 g / eq. It is further preferred that

The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The molecular weight (weight average molecular weight in the case of a polymer) of the epoxy compound is preferably 200 to 100,000, and more preferably 500 to 50,000. 3000 or less is preferable, as for the upper limit of molecular weight (in the case of a polymer, weight average molecular weight), 2000 or less is more preferable, and 1500 or less is still more preferable.

The epoxy compounds are compounds described in paragraphs 0034 to 0036 in JP 2013-011869A, paragraphs 0147 to 0156 in JP 2014-043556 A, and paragraphs 0085 to 0092 in JP 2014-089408 A. Can also be used. The contents of these are incorporated herein.

When the coloring composition of the present invention contains an epoxy compound, the content of the epoxy compound is preferably 0.1 to 40% by mass in the total solid content of the coloring composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less. The epoxy compounds may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a sum becomes said range.

<< solvent >>
The coloring composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied.

Examples of the organic solvent include, for example, the following organic solvents. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyl oxyacetate alkylate (Eg, methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ethyl, 3-ethoxypropionate etc.), 2-alkyloxypropionic acid alkyl esters (eg methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate etc. (eg Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and Ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, Acetoacetate Le, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like can be mentioned. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. Preferred examples of the aromatic hydrocarbons include toluene and xylene. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of solubility improvement. The organic solvents may be used alone or in combination of two or more. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene etc.) as a solvent due to environmental reasons etc. (For example, 50 mass ppm (parts per part of the total amount of organic solvent) or less, 10 mass ppm or less, or 1 mass ppm or less).

The organic solvents may be used alone or in combination of two or more. When two or more organic solvents are used in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate is particularly preferable. 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, and a mixed solution composed of two or more kinds.

In the present invention, it is preferable to use a solvent having a low metal content as the solvent. The metal content in the solvent is preferably, for example, 10 parts by weight (pps) or less. If necessary, a solvent having a metal content of mass ppt (parts per trillion) level may be used, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Journal, November 13, 2015) Day).

As a method of removing impurities such as metal from the solvent, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter can be mentioned. As a filter hole diameter of a filter used for filtration, 10 micrometers or less are preferred, 5 micrometers or less are more preferred, and 3 micrometers or less are still more preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one type of isomer may be contained, or two or more types may be contained.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

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

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

As a thiol compound, the polyfunctional thiol compound etc. which have a 2 or more mercapto group in a molecule | numerator are mentioned. The polyfunctional thiol compound may be added for the purpose of improving the stability, the odor, the resolution, the developability, the adhesion and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound having a structure represented by the following formula (T1).
Formula (T1)

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

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

Further, as the curing accelerator, methylol compounds (for example, compounds exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, Curing agent described in paragraph 0186 of JP2013-41165A, base generator (for example, ionic compound described in JP2014-55114A), isocyanate compound (for example, JP2012-150180A) Compounds described in paragraph 0071 of the gazette, alkoxysilane compounds (eg, alkoxysilane compounds having an epoxy group described in JP-A-2011-253054), onium salt compounds (eg, JP-A-2015-34963) It is illustrated as an acid generator in paragraph No. 0216 Compounds, compounds described in JP-A-2009-180949) or the like can be used.

When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass in the total solid content of the coloring composition, and is 0.8 to 6.4. % By mass is more preferred.

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

The chromophores constituting the pigment derivative include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone compound Skeletons, perylene skeletons, thioindigo skeletons, isoindoline skeletons, isoindolinone skeletons, quinophthalone skeletons, threne skeletons, metal complex skeletons, etc., and quinoline skeletons, benzimidazolone skeletons, diketo A pyrrolopyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a benzimidazolone skeleton are more preferable. As an acid group which a pigment derivative has, a sulfo group and a carboxyl group are preferred, and a sulfo group is more preferred. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable. As a specific example of the pigment derivative, for example, the description in paragraphs [0162] to [0182] of JP-A-2011-252065 can be referred to, and the contents thereof are incorporated in the present specification.

When the coloring composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. The pigment derivative may use only 1 type and may use 2 or more types together.

<< Surfactant >>
The coloring composition of the present invention preferably contains a surfactant. As the surfactant, various surfactants such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants can be used to further improve the coating property. Fluorinated surfactants are preferred because they can be used.

By containing a fluorine-based surfactant in the coloring composition of the present invention, liquid properties when prepared as a coating liquid can be improved, and uniformity of coating thickness can be further improved. That is, in the case of film formation using a coating solution to which a coloring composition containing a fluorine-based surfactant is applied, the interfacial tension on the surface of the coating film is reduced, and the uniformity of drying is improved. For this reason, film formation with few coating nonuniformity can be performed more suitably.

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

As fluorine-based surfactants, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, R304, F437, F475, F479, F482, F554, F780 (all, DIC Corporation) , Florard FC430, FC431, FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (all, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (all, manufactured by OMNOVA) and the like. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, and compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used.

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

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant. Such fluorine-based surfactants can be referred to the description of JP-A-2016-216602, the contents of which are incorporated herein.

As the fluorine-based surfactant, a block polymer can also be used. For example, compounds described in JP-A-2011-89090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) (meth) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorinated surfactant used in the present invention. In the following formulas,% indicating the proportion of repeating units is mol%.

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

A fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965. Examples of commercially available products include Megafac RS-101, RS-102, RS-718-K, RS-72-K and the like manufactured by DIC Corporation.

As nonionic surfactants, glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company), Tetronics 304, 701, 704, 901, 904, 150R1 (BA). Made by F company, Solsparse 20000 (made by Nippon Lubrisol Ltd.), NCW-101, NCW-1001, NCW-1002 (made by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.), and the like.

As a cationic surfactant, KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 1; 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

As silicone type surfactant, for example, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (more than Toray Dow Corning ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, Momentive Performance Materials Co., Ltd.), KP-341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) Made, BYK 307, BYK 323, BYK 330 (above, made by Big Chemie Co., Ltd.), etc. are mentioned.

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

<< UV Absorbent >>
The coloring composition of the present invention can contain an ultraviolet absorber. As the ultraviolet light absorber, conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds and the like can be used. The details of these can be referred to the descriptions of paragraphs 0052 to 0072 of JP 2012-208374 A and paragraphs 0317 to 0334 of JP 2013-68814 A, the contents of which are incorporated herein. Specific examples of the ultraviolet absorber include compounds having the following structure. Examples of commercially available ultraviolet light absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). In addition, as the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) made by Miyoshi Yushi may be used.

When the coloring composition of the present invention contains a UV absorber, the content of the UV absorber is preferably 0.1 to 10% by mass, and more preferably 0.1 to 5% by mass in the total solid content of the coloring composition. More preferably, 0.1 to 3% by mass is particularly preferable. Moreover, an ultraviolet absorber may use only 1 type and may use 2 or more types. When 2 or more types of ultraviolet absorbers are contained, it is preferable that the total amount of them becomes the said range.

<< Silane coupling agent >>
The coloring composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example.

The silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, an ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. The silane compound which has and is preferable. Specific examples of the silane coupling agent include, for example, N-β-aminoethyl-γ-aminopropylmethyl dimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-602), N-β-aminoethyl-γ-aminopropyl tri- trile Methoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-602), γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., KBM-903), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503), 3- 3- Examples thereof include glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) and the like. The details of the silane coupling agent can be referred to the description of Paragraph Nos. 0155 to 0158 of JP 2013-254047 A, the contents of which are incorporated herein.

When the coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass, and 0.01 to 10% by mass in the total solid content of the coloring composition. % Is more preferable, and 0.1 to 5% by mass is particularly preferable. The coloring composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When 2 or more types of silane coupling agents are contained, it is preferable that the total amount of them becomes the said range.

<< polymerization inhibitor >>
The coloring composition of the present invention can contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts etc.) and the like.
When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass in the total solid content of the coloring composition. The coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When it contains two or more types, it is preferable that the total amount of them becomes the said range.

<< Other Additives >>
In the coloring composition of the present invention, various additives such as a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor and the like can be blended, if necessary. Examples of these additives include the additives described in paragraphs [0155] to [0156] of JP-A-2004-295116, the contents of which are incorporated herein. Further, as the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0042 of JP-A-2011-90147), a thioether compound or the like can be used. As a commercial item, for example, Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60G, AO-60, AO-80, AO-A manufactured by ADEKA Co., Ltd.) 330). One type of antioxidant may be used or two or more types may be used. The coloring composition of the present invention can contain the sensitizer and the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the same publication.

Although the metallic composition may be contained in the coloring composition depending on the raw materials used, etc., the content of the Group 2 element (such as calcium and magnesium) in the coloring composition is 50 mass ppm or less from the viewpoint of suppression of defect generation and the like. Is preferably 0.01 to 10 ppm by mass. Further, the total amount of the inorganic metal salt in the coloring composition is preferably 100 mass ppm or less, and more preferably 0.5 to 50 mass ppm.

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

The solid content concentration of the coloring composition of the present invention is preferably 10 to 25% by mass. The upper limit is preferably 23% by mass or less, and more preferably 20% by mass or less. The lower limit is preferably 12% by mass or more, and more preferably 14% by mass or more.

The coloring composition of the present invention can be used with its viscosity adjusted for the purpose of adjusting the film surface state (flatness and the like), adjusting the film thickness, and the like. The value of viscosity can be appropriately selected as necessary, and for example, 0.3 to 50 mPa · s at 25 ° C. is preferable, and 0.5 to 20 mPa · s is more preferable. As a method of measuring the viscosity, for example, using a Toki Sangyo viscometer RE85L (rotor: 1 ° 34 ′ × R24, measurement range 0.6 to 1200 mPa · s) and performing temperature control at 25 ° C. It can be measured.

The coloring composition of the present invention, using a rotating viscometer, on the viscosity mu ₁ at 23 ° C. when measured at a shear rate of 10s ^-1, the viscosity at 23 ° C. when measured at a shear rate of 1000 s ^-1 mu it is preferable ₂ mu ₂ / mu ₁ is the ratio is 0.75 to 1.25. μ ₂ / μ ₁ is preferably 0.90 or more, and more preferably 0.95 or more. Further, μ ₂ / μ ₁ is preferably 1.10 or less, more preferably 1.05 or less. If μ ₂ / μ ₁ is in the above range, the coatability is good, and a film in which the thickness unevenness is suppressed can be formed. As a method of adjusting μ ₂ / μ ₁ of the coloring composition to the above range, the solid content concentration of the coloring composition, the content of the pigment (DPP), the content of the graft resin A, etc. are appropriately adjusted. It can be adjusted to the range. For example, when it is desired to reduce μ ₂ / μ ₁ of the coloring composition within the above range, a method of decreasing the solid content concentration of the coloring composition to the lower limit of the above range may be mentioned. Moreover, when it is desired to increase μ ₂ / μ ₁ of the coloring composition within the above range, there is a method of increasing the solid content concentration of the coloring composition to the upper limit of the above range.

There is no limitation in particular as a storage container of the coloring composition of this invention, A well-known storage container can be used. In addition, as a container, for the purpose of suppressing the mixing of impurities into the raw materials and the composition, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin or a bottle in which six types of resin are seven layers It is also preferred to use. As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.

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

When the coloring composition of the present invention is used as a color filter for liquid crystal display applications, the voltage holding ratio of the liquid crystal display device provided with the color filter is preferably 70% or more, more preferably 90% or more . Known means for obtaining high voltage holding ratio can be suitably incorporated, and typical means include use of a high purity material (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition Can be mentioned. The voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of JP-A-2011-008004 and paragraph 0123 to 0129 of JP-A-2012-224847.

<Method of Preparing Colored Composition>
The coloring composition of the present invention can be prepared by mixing the above-mentioned components. In preparation of the coloring composition, all the components may be simultaneously dissolved and / or dispersed in a solvent to prepare a coloring composition, and if necessary, each component may be used as two or more solutions or dispersions as appropriate. Alternatively, they may be mixed at the time of use (at the time of application) to prepare a coloring composition.

Moreover, it is preferable to include the process of disperse | distributing a pigment in preparation of a coloring composition. In the process of dispersing the pigment, mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. In the pulverization of the pigment in a sand mill (bead mill), it is preferable to use a bead having a small diameter, and to process under conditions in which the pulverization efficiency is enhanced by increasing the packing ratio of the beads. Moreover, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverizing treatment. In addition, the process and the dispersing machine for dispersing the pigment are the dispersion technology and industrial application centering on “Dispersion Technology Complete, Information Technology Co., Ltd. issued July 15, 2005” and “suspension (solid / liquid dispersion system)” The process and the dispersing machine described in Paragraph No. 0022 of JP-A-2015-157893, published on October 10, 1978, can be suitably used. Further, in the process of dispersing the pigment, the particles may be subjected to a refinement treatment in a salt milling step. The materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-04629.

In preparation of a coloring composition, it is preferable to filter with a filter for the purpose of the removal of a foreign material, reduction of a defect, etc. As a filter, if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular. For example, a fluorine resin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, nylon-6, 6), a polyolefin resin such as polyethylene or polypropylene (PP) (high density and / or super A filter using a material such as a high molecular weight polyolefin resin) can be mentioned. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.

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

Moreover, it is also preferable to use the filter using a fiber-like filter medium as a filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specific examples of the filter using a fiber-like filter medium include filter cartridges of SBP type series (SBP 008, etc.), TPR type series (TPR 002, TPR 005, etc.), and SHPX type series (SHPX 003, etc.) manufactured by Loki Techno. .

When using filters, different filters may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
For example, filters of different pore sizes may be combined within the range described above. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it is possible to select from various filters provided by Nippon Pall Co., Ltd. (DFA 4201 NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. can do.
Moreover, filtration with a 1st filter may be performed only with a dispersion liquid, and you may filter with a 2nd filter, after mixing other components. As the second filter, one formed of the same material as the first filter can be used.

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

<Pattern formation method>
Next, the pattern formation method of the present invention will be described. The pattern forming method of the present invention comprises the steps of: forming a colored composition layer on a support using the above-mentioned coloring composition of the present invention; exposing the colored composition layer in a pattern (exposure step); And (d) developing and removing the unexposed area of the colored composition layer in this order. Each step will be described below.

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

There is no limitation in particular as a support body, According to a use, it can select suitably. For example, a glass substrate, a substrate for a solid-state imaging device provided with a solid-state imaging device (light receiving device) such as a CCD or a CMOS, a silicon substrate, etc. may be mentioned. Moreover, on these substrates, if necessary, a subbing layer may be provided to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the surface.

As a method of applying the coloring composition on the support, a spin coating method, a slit coating method, an inkjet method and the like can be mentioned, and the spin coating method is preferable because the effect of the present invention is more remarkably exhibited. The coating conditions in the spin coating method vary depending on the solid content concentration of the coloring composition and the like. For example, spin coating is preferably performed at a rotational speed of 300 to 3000 rpm, and spin coating at a rotational speed of 800 to 1500 rpm Is more preferred. If it is this range, it is easy to manufacture the cured film in which the thickness nonuniformity was suppressed.

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

<< exposure step >>
Next, the colored composition layer is exposed in a pattern (exposure step). For example, pattern exposure can be performed by exposing the coloring composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, the exposed portion can be cured. As radiation (light) which can be used at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed under the atmosphere, for example, under a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially It may be exposed with no oxygen, and may be exposed under a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. The exposure intensity is can be set appropriately, usually ^{^{1000W / m 2 ~ 100000W / m}} 2 ( ^{e.g., 5000W / m 2, 15000W /} m 2, or, 35000W / ^{m 2)} selected from the range of Can. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / ^{m 2.}

<< Development Process >>
Next, the unexposed area of the colored composition layer is removed by development to form a pattern. The development removal of the unexposed part of a coloring composition layer can be performed using a developing solution. As a result, the colored composition layer in the unexposed area in the exposure step is eluted into the developer, and only the photocured area remains. As a developing solution, an organic alkaline developing solution which does not cause damage to a solid-state imaging device or circuit of a base is desirable. The temperature of the developing solution is preferably, for example, 20 to 30.degree. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of the residue, the process of shaking off the developer every 60 seconds and supplying the developer anew may be repeated several times.

As a developing solution, an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferably used. Examples of the alkaline agent include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide. Organic alkaline compounds such as benzyl, trimethyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, or water Inorganic materials such as sodium oxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate Potassium compounds may be mentioned. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. As an example of surfactant, the surfactant mentioned above is mentioned and nonionic surfactant is preferable. The developer may be prepared once as a concentrate and diluted to a concentration required for use, from the viewpoint of transportation and storage convenience. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) by a pure water after image development. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) with a pure water after image development.

After development, it is preferable to carry out heat treatment (post bake) after drying. Post-baking is a heat treatment after development to complete curing, and the heating temperature is, for example, preferably 100 to 240 ° C., and more preferably 200 to 240 ° C. When the support on which the cured film is formed includes an organic electroluminescent (organic EL) element, an image sensor having a photoelectric conversion film made of an organic material, and the like, the post-baking temperature is 150 ° C. or less Is preferred. The lower limit can be, for example, 50 ° C. or higher. Post-baking is performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulating dryer), high frequency heater or the like so that the film (cured film) after development becomes the above conditions. It can be carried out.
The pattern formation method may include a process by dry etching. As the dry etching process, for example, the dry etching process described in paragraph 0137 to paragraph 0165 of International Publication WO 2018/061781 can be mentioned.

The cured film preferably has high flatness. Specifically, the surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and still more preferably 15 nm or less. The lower limit is not defined, but is preferably, for example, 0.1 nm or more. The surface roughness can be measured, for example, using an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco.
Further, the contact angle of water on the cured film can be appropriately set to a preferable value, but is typically in the range of 50 to 110 °. The contact angle can be measured, for example, using a contact angle meter CV-DT · A type (manufactured by Kyowa Interface Science Co., Ltd.).

It is desirable that the volume resistivity of each pattern (pixel) be high. 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 10 ¹⁴ Ω · cm or less, for example. The volume resistance value of the pixel can be measured, for example, using 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 cured film of the present invention described above. In the color filter of the present invention, the thickness of the cured film can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more. The color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) or an image display device.

<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 imaging device of the present invention is not particularly limited as long as the cured film of the present invention is provided and functions as a solid-state imaging device, and examples thereof include the following configurations.

On the substrate, there are a plurality of photodiodes forming the light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and transfer electrodes made of polysilicon etc. Device protective film formed of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. And has a color filter on the device protection film. Furthermore, the device has a light collecting means (for example, a micro lens etc., hereinafter the same) on the device protective film and under the color filter (closer to the substrate) or a structure having the light collecting means on the color filter It may be. In addition, the color filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned into, for example, a grid shape by partition walls. The partition walls in this case preferably have a low refractive index for each colored pixel. As an example of an imaging device having such a structure, devices described in JP 2012-227478 A and JP 2014-179577 A can be mentioned. The imaging device provided with the solid-state imaging device according to the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an imaging function, but also for in-vehicle cameras and surveillance cameras.

<Image display device>
The cured film of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device. For the definition of the image display device and details of each image display device, for example, “Electronic display device (authored by Akio Sasaki, Inc., Industrial Research Association, published in 1990)”, “Display device (authored by Ibuki, industrial book ( Co., Ltd., published in Heisei 1973). The liquid crystal display device is described, for example, in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Association, Inc., 1994)". There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

The present invention will be specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.

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

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

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

(Pigment)
PR254: C.I. I. Pigment red 254 (pigment represented by the formula (DPP))
PR 255: C.I. I. Pigment red 255 (pigment represented by formula (DPP))
PR 272: C.I. I. Pigment red 272 (pigment represented by the formula (DPP))
PO71: C.I. I. Pigment orange 71 (pigment represented by the formula (DPP))
PO 73: C.I. I. Pigment orange 73 (pigment represented by the formula (DPP))
PY 139: C.I. I. Pigment yellow 139 (pigments other than pigments represented by the formula (DPP))

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

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

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

(Polymerizable compound)
E-1: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
E-2: Alonics 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)
F-2: IRGACURE-OXE02 (manufactured by BASF)

(Surfactant)
G-1: The following compound (Mw = 14000). In the following formulas,% indicating the proportion of repeating units is mol%.

(UV absorber)
H-1: UV-503 (made by Daito Chemical Industries)

<Evaluation>
(Measurement of viscosity ratio μ ₂ / μ ₁ )
When the coloring composition immediately after preparation is measured using a rotational viscometer (MCR 301, manufactured by Anton Paar) and measured at a shear rate of 1000 s ^-1 with respect to the viscosity μ ₁ at 23 ° C. measured at a shear rate of 10 s ^-1 The ratio of the viscosity μ ₂ at 23 ° C. (μ ₂ / μ ₁ ) was measured.

(Evaluation of uneven thickness)
Apply spin coating (rotational speed = 1050 rpm) to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the film thickness after prebaking becomes 0.64 μm, and then 100 Heat treatment (prebake) was performed for 120 seconds using a hot plate of 0 ° C. Thereafter, the film was further heated at 200 ° C. for 300 seconds using a hot plate to form a cured film.
Regarding the film thickness of the obtained cured film, using an optical film thickness meter (F50, manufactured by Filmetrics), measure the film thickness of 13 points at equal intervals in the outer periphery-center-outer periphery direction (diameter direction) of an 8-inch wafer Then, the difference (Δt) between the maximum value and the minimum value of the film thickness was determined. The unevenness in thickness was evaluated using the value of Δt. The smaller the Δt, the smaller the thickness unevenness.

As shown in the above table, in the example, Δt was small, and thickness unevenness was suppressed. In particular, C.I. I. In Example 1 using pigment red 254, thickness unevenness could be significantly suppressed.

Claims

It is a coloring composition containing a pigment represented by Formula (DPP), a resin, a photopolymerization initiator, and a polymerizable compound,
The resin includes a graft resin having a poly (meth) acrylate structure as a main chain and containing 20 mol% or more of a repeating unit A having a graft chain of a polyester structure in a side chain,
A coloring composition in which 60% by mass or more of the resin contained in the coloring composition is the graft resin;
Formula (DPP)

In the formula, R 1 and R 2 are each independently 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 Represents
R D1 and R D2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
m1 and m2 each independently represent an integer of 0 to 5,
When m1 is 2 or more, the m1 R 1 s may be identical to or different from each other,
If m2 is 2 or more, may be respectively m2 one of R 2 identical or different.
The pigment represented by the above formula (DPP) is at least one selected from color index pigment red 254, color index pigment red 255, color index pigment red 272, color index pigment orange 71, and color index pigment orange 73 The coloring composition according to claim 1.
The coloring composition according to claim 1 or 2, wherein the graft chain is a structure represented by Formula (G-1), Formula (G-2) or Formula (G-3);

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 coloring composition according to any one of claims 1 to 3, wherein the graft chain comprises a polyester structure derived from a compound selected from ε-caprolactone and δ-valerolactone.
The coloring composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the repeating unit A is 1,000 or more.
The coloring composition according to any one of claims 1 to 5, wherein the polymerizable compound comprises a polymerizable compound having an acid group.
The coloring composition according to any one of claims 1 to 6, wherein the content of the polymerizable compound is 100 parts by mass or less with respect to 100 parts by mass of the graft resin.
The coloring composition according to any one of claims 1 to 7, wherein the content of the graft resin is 30 to 90 parts by mass with respect to 100 parts by mass of the pigment represented by the formula (DPP).
Using a rotary viscometer for viscosity mu 1 at 23 ° C. when measured at a shear rate of 10s -1, the ratio of the viscosity mu 2 at 23 ° C. when measured at a shear rate of 1000s -1 μ 2 / The coloring composition according to any one of claims 1 to 8, wherein μ 1 is 0.75 or more and 1.25 or less.
A cured film obtained by curing the coloring composition according to any one of claims 1 to 9.
Forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 9;
Exposing the colored composition layer in a pattern;
Developing and removing the unexposed area of the colored composition layer;
A pattern forming method including:
A color filter comprising the cured film according to claim 10.
The solid-state image sensor which has a cured film of Claim 10.
The image display apparatus which has a cured film of Claim 10.