TWI695037B - Colored composition, color filter, method for forming pattern, method for manufacturing color filter, solid-state image sensor, image display device and method for producing dye multimer - Google Patents

Abstract

A colored composition includes a dye multimer represented by general formula (1) and a polymerizable compound, wherein in general formula (1), P represents an n-valent linking group, Q represents a polymer chain containing a repeating unit that has a dye structure, an average number of the repeating units having a dye structure is 2 or more, and n represents an integer of 3 to 10.   P-(Q)_n …(1)

Description

Coloring composition, color filter, pattern forming method, method of manufacturing color filter, solid-state imaging element, image display device, and method of manufacturing pigment polymer

The invention relates to a coloring composition. In particular, it relates to a coloring composition suitable for color filters used in solid-state imaging devices, image display devices, and the like. In addition, the present invention relates to a color filter, a solid-state imaging element, and an image display device using a coloring composition. In addition, the present invention also relates to a method of forming a pattern using a colored composition, a method of manufacturing a color filter, and a method of manufacturing a dye multimer.

In recent years, the popularity of factor cameras and mobile phones with cameras has increased the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors. As a key device of these displays or optical elements, a color filter is used, and the demand for higher sensitivity and miniaturization is further increased. Such a color filter usually has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and functions to decompose transmitted light into three primary colors.

The coloring agents used in the color filters are required to have the following properties. That is, it is necessary to have good light absorption characteristics in terms of color reproducibility, and good light resistance.

On the other hand, Patent Literature 1 discloses a pigment dispersant that contains 2 to 9 sites having adsorption properties for pigments in one molecule. Examples of the sites having adsorption properties for pigments include organic pigment structures, heterocyclic structures, acidic groups, groups with basic nitrogen atoms, urea groups, carbamate groups, and groups with coordination oxygen atoms. , Hydrocarbon groups with 4 or more carbon atoms, alkoxysilane groups, epoxy groups, isocyanate groups, hydroxyl groups, ionic functional groups, etc. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-222950

[Problems to be solved by the invention]

In coloring compositions used for color filters and the like, further improvements in light resistance, color shifting, and flatness are required. In addition, Patent Document 1 relates to an invention of a pigment dispersant. Patent Document 1 describes that an organic dye structure can be used as a site having adsorption performance for pigments, but the pigment dispersant preferably has no color, and therefore a structure having low absorbance must be selected for the site having adsorption performance for pigments. In addition, in Patent Document 1, there is no description as a motivation for using a pigment dispersant as a colorant.

The present invention was made in view of the above circumstances, and an object thereof is to provide a coloring composition excellent in light resistance, color shift property, and flatness. In addition, an object of the present invention is to provide a color filter, a pattern forming method, a method of manufacturing a color filter, a solid-state imaging element, an image display device, and a method of manufacturing a dye polymer. [Means to solve the problem]

通式（2）中，A¹ 表示n價的連結基， B¹ 表示單鍵、-O-、-S-、-CO-、-NR-、-O₂ C-、-CO₂ -、-NROC-、或-CONR-， R表示氫原子、烷基或芳基， C¹ 表示單鍵或二價的連結基， S表示硫原子， Q表示含有具有色素結構的重複單元的聚合物鏈， n個Q的具有色素結構的重複單元的個數的平均值為兩個以上， n表示3～10的整數。 ＜3＞ 如＜2＞所述的著色組成物，其中A¹ 為包含選自主鏈上可具有氧原子的脂肪族烴基、芳香族環基及雜環基中的一種或兩種以上的組合的基。 ＜4＞ 如＜1＞至＜3＞中任一項所述的著色組成物，其中色素多聚體於400 nm～800 nm內的最大吸收波長中的由下述式（Aλ）所表示的比吸光度為5以上；   E=A/（c×l）···（Aλ）   式（Aλ）中，E表示於400 nm～800 nm內的最大吸收波長中的比吸光度， A表示於400 nm～800 nm內的最大吸收波長中的吸光度， l表示單位由cm表示的單元長度， c表示單位由mg/ml表示的溶液中的色素多聚體的濃度。 ＜5＞ 如＜1＞至＜4＞中任一項所述的著色組成物，其中相對於著色組成物的總固體成分，含有色素多聚體1質量%～50質量%。 ＜6＞ 如＜1＞至＜5＞中任一項所述的著色組成物，其中色素多聚體為使由通式（3）所表示的化合物、與具有色素結構及自由基聚合性基的化合物進行自由基聚合所獲得者。   P⁰ -(SH)_n ···（3）   通式（3）中，P⁰ 表示n價的連結基， SH表示硫醇基， n表示3～10的整數。 ＜7＞ 如＜1＞至＜6＞中任一項所述的著色組成物，其更包括色素多聚體以外的色素。 ＜8＞ 如＜1＞至＜7＞中任一項所述的著色組成物，其更包括光聚合起始劑。 ＜9＞ 如＜1＞至＜8＞中任一項所述的著色組成物，其中Q具有源自選自三芳基甲烷色素、呫噸色素、蒽醌色素、花青色素、方酸內鎓鹽色素、喹酞酮色素、酞菁色素、亞酞菁色素、偶氮色素及二吡咯亞甲基色素中的色素的色素結構。 ＜10＞ 如＜1＞至＜9＞中任一項所述的著色組成物，其中Q含有選自具有酸基的重複單元及具有聚合性基的重複單元中的一種以上。 ＜11＞ 如＜1＞至＜10＞中任一項所述的著色組成物，其中Q為選自(甲基)丙烯酸系樹脂、苯乙烯系樹脂、及(甲基)丙烯酸/苯乙烯系樹脂中的一種。 ＜12＞ 一種彩色濾光器，其使用如＜1＞至＜11＞中任一項所述的著色組成物而形成。 ＜13＞ 一種圖案形成方法，其包括：將如＜1＞至＜11＞中任一項所述的著色組成物應用於支撐體上來形成著色組成物層的步驟；將著色組成物層曝光成圖案狀的步驟；以及將曝光成圖案狀的所述著色組成物層的未曝光部顯影去除而形成著色圖案的步驟。 ＜14＞ 一種圖案形成方法，其包括：將如＜1＞至＜11＞中任一項所述的著色組成物應用於支撐體上來形成著色組成物層，並使其硬化而形成著色層的步驟；於著色層上形成光阻劑層的步驟；藉由進行曝光及顯影來將光阻劑層加以圖案化而獲得抗蝕劑圖案的步驟；以及將抗蝕劑圖案作為蝕刻遮罩來對著色層進行乾式蝕刻而形成著色圖案的步驟。 ＜15＞ 一種彩色濾光器的製造方法，其包括如＜13＞或＜14＞所述的圖案形成方法。 ＜16＞ 一種固態攝影元件，其包括如＜12＞所述的彩色濾光器、或藉由如＜15＞所述的彩色濾光器的製造方法所獲得的彩色濾光器。 ＜17＞ 一種影像顯示裝置，其包括如＜12＞所述的彩色濾光器、或藉由如＜15＞所述的彩色濾光器的製造方法所獲得的彩色濾光器。 ＜18＞ 一種色素多聚體的製造方法，其包括使由通式（3）所表示的化合物、與具有色素結構及自由基聚合性基的化合物進行自由基聚合。   P⁰ -(SH)_n ···（3）   通式（3）中，P⁰ 表示n價的連結基， SH表示硫醇基， n表示3～10的整數。 [發明的效果]As a result of detailed investigations by the present inventors, it has been found that by using a pigment polymer in which n polymer chains containing a repeating unit having a pigment structure are bonded to an n-valent linking group, light resistance and color shift can be obtained The present invention has been completed by a coloring composition excellent in properties and flatness. Therefore, the present invention provides the following. <1> A coloring composition including a pigment polymer represented by the general formula (1) and a polymerizable compound; P-(Q) _n ··· (1) In the general formula (1), P represents An n-valent linking group, Q represents a polymer chain containing a repeating unit having a dye structure, the average number of n Q repeating units having a dye structure is two or more, and n represents an integer of 3-10. <2> The coloring composition as described in <1>, wherein the pigment polymer represented by the general formula (1) is represented by the general formula (2);

In the general formula (2), A ¹ represents an n-valent linking group, and B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -,- NROC- or -CONR-, R represents a hydrogen atom, an alkyl group or an aryl group, C ¹ represents a single bond or a divalent linking group, S represents a sulfur atom, and Q represents a polymer chain containing a repeating unit having a pigment structure, The average value of the number of n Q repeating units having a dye structure is two or more, and n represents an integer of 3-10. <3> The coloring composition according to <2>, wherein A ¹ is one or a combination of two or more selected from aliphatic hydrocarbon groups, aromatic ring groups, and heterocyclic groups that may have an oxygen atom in the main chain base. <4> The coloring composition according to any one of <1> to <3>, in which the maximum absorption wavelength of the pigment polymer in the range of 400 nm to 800 nm is represented by the following formula (Aλ) The specific absorbance is 5 or more; E=A/(c×l)... (Aλ) In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength within 400 nm to 800 nm, and A represents 400 nm The absorbance at the maximum absorption wavelength within ~800 nm, l represents the unit length in cm and c represents the concentration of the pigment polymer in the solution in mg/ml. <5> The coloring composition according to any one of <1> to <4>, wherein the coloring polymer contains 1% by mass to 50% by mass relative to the total solid content of the coloring composition. <6> The coloring composition according to any one of <1> to <5>, wherein the pigment polymer is a compound represented by the general formula (3) and has a pigment structure and a radical polymerizable group The compound obtained by radical polymerization. P ⁰ -(SH) _n (3) In the general formula (3), P ⁰ represents an n-valent linking group, SH represents a thiol group, and n represents an integer of 3-10. <7> The coloring composition according to any one of <1> to <6>, which further includes a pigment other than the pigment polymer. <8> The coloring composition according to any one of <1> to <7>, which further includes a photopolymerization initiator. <9> The coloring composition according to any one of <1> to <8>, wherein Q has a source derived from a triarylmethane pigment, a xanthene pigment, an anthraquinone pigment, a cyanine pigment, a squarylium The pigment structure of the pigment in the salt color, quinophthalone color, phthalocyanine color, subphthalocyanine color, azo color, and dipyrromethene color. <10> The coloring composition according to any one of <1> to <9>, wherein Q contains one or more kinds selected from a repeating unit having an acid group and a repeating unit having a polymerizable group. <11> The coloring composition according to any one of <1> to <10>, wherein Q is selected from (meth)acrylic resins, styrene resins, and (meth)acrylic/styrene resins One of resins. <12> A color filter formed using the coloring composition according to any one of <1> to <11>. <13> A pattern forming method, comprising: applying the coloring composition as described in any one of <1> to <11> to a support to form a coloring composition layer; exposing the coloring composition layer to A pattern-like step; and a step of developing and removing the unexposed portion of the colored composition layer exposed in a pattern to form a colored pattern. <14> A pattern forming method including: applying the coloring composition as described in any one of <1> to <11> to a support to form a coloring composition layer, and hardening it to form a coloring layer Step; forming a photoresist layer on the colored layer; step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etching mask The step of dry etching the colored layer to form a colored pattern. <15> A method for manufacturing a color filter, including the pattern forming method described in <13> or <14>. <16> A solid-state imaging element including the color filter described in <12> or the color filter obtained by the method for manufacturing a color filter described in <15>. <17> An image display device including the color filter described in <12> or the color filter obtained by the method of manufacturing a color filter described in <15>. <18> A method for producing a dye polymer, which includes radically polymerizing a compound represented by the general formula (3) and a compound having a dye structure and a radical polymerizable group. P ⁰ -(SH) _n (3) In the general formula (3), P ⁰ represents an n-valent linking group, SH represents a thiol group, and n represents an integer of 3-10. [Effect of invention]

According to the present invention, it is possible to provide a coloring composition excellent in light resistance, color shift and flatness. In addition, a method for manufacturing a color filter, a pattern forming method, a method for manufacturing a color filter, a solid-state imaging element, an image display device, and a dye polymer can be provided.

Hereinafter, the content of the present invention will be described in detail. In the description of the group (atom group) in this specification, the unrepresented and unsubstituted expression includes a group (atom group) without a substituent, and also includes a group (atom group) with a substituent. For example, the so-called "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group), but also a substituted alkyl group (substituted alkyl group). In this specification, light refers to actinic rays or radiation. In addition, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (Extreme Ultraviolet (EUV) light), X-rays, and electron beams Wait. In this manual, unless otherwise specified, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far-ultraviolet rays represented by an excimer laser, X-rays, EUV light, etc., but also using electron beams, ions Drawing by particle beams such as beams is also included in the exposure. In this specification, the numerical range indicated by "~" refers to a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In this specification, the total solid content refers to the total mass of components after removing the solvent from the total composition of the coloring composition. In this specification, "(meth)acrylate" means both or either of acrylate and methacrylate, and "(meth)acrylate" means both of acrylate and methacrylate, Or any one, "(meth)allyl" means both allyl and methallyl, or any one, "(meth)acryl acetyl" means propylene acetyl and methacrylic Either of the two, or either. In this specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group participating in a polymerization reaction. In this specification, Me in the chemical formula represents methyl, Et represents ethyl, Pr represents propyl, Bu represents butyl, and Ph represents phenyl. In this specification, the term "step" not only refers to an independent step, but even in the case where it cannot be clearly distinguished from other steps, as long as the expected effect of the step is achieved, it is also included in this term. In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (Gel Permeation Chromatography, GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh (shares)) and using TSKgel SuperAWM-H (Made by Tosoh Corporation, 6.0 mm ID (Inner Diameter, ID) × 15.0 cm) Used as a column, used 10 mmol/L lithium bromide N-Methylpyrrolidinone (NMP) solution For dissolution.

<Coloring composition> The coloring composition of the present invention contains a pigment polymer represented by the general formula (1) described later and a polymerizable compound. By setting it as the said structure, the coloring composition excellent in light resistance, color shift property, and flatness can be provided. The reason why such an effect is obtained is not clear, but it can be considered that the pigment multimer represented by the general formula (1) described later is bound to an n-valent link by n polymer chains containing a repeating unit having a pigment structure. Basically, it is possible to reduce the entanglement of polymer chains having a pigment structure compared to a pigment polymer having a linear structure. Therefore, it is considered that the pigment polymer is hard to aggregate and a film with excellent flatness can be obtained. In addition, it is considered that since the dye structure is introduced into the polymer chain, it is difficult for the dye to diffuse and the color shift property is also excellent. In addition, it is considered that by making the pigment multimer, the adsorption performance with other molecules such as pigments is improved, and it is easy to cause energy movement between the molecules, thereby also being excellent in light resistance. In addition, for example, when patterning is performed by photolithography, the entanglement of polymer chains having a pigment structure can be reduced, so that the penetration of the developer can be improved, the development speed is fast, and the development residue can also be difficult produce. Hereinafter, the present invention will be described in detail.

<<Dye multimer represented by general formula (1)>> The coloring composition of the present invention contains a dye multimer represented by the following general formula (1) (hereinafter, sometimes simply referred to as "pigment multimer" Body (A)").

The pigment polymer (A) preferably has a maximum absorption wavelength in the range of 400 nm to 800 nm. In the coloring composition of the present invention, the pigment polymer (A) functions as a colorant, for example.

P-(Q) _n ··· (1) In the general formula (1), P represents an n-valent linking group, Q represents a polymer chain containing a repeating unit having a dye structure, and n Q repeats having a dye structure The average value of the number of units is two or more, and n represents an integer of 3-10.

<<<Linking group P>>> In the general formula (1), P represents an n-valent linking group. The n-valent linking group includes those containing 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms The group may be unsubstituted or may further have a substituent. The n-valent linking group represented by P preferably contains 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 A group of sulfur atoms. More preferably, it is a group containing 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms. Even more preferably, it is a group containing 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms. The n-valent linking group represented by P is preferably a linking group derived from a polyol.

通式（2）中，A¹ 表示n價的連結基， B¹ 表示單鍵、-O-、-S-、-CO-、-NR-、-O₂ C-、-CO₂ -、-NROC-、或-CONR-， R表示氫原子、烷基或芳基， C¹ 表示單鍵或二價的連結基， S表示硫原子， Q表示含有具有色素結構的重複單元的聚合物鏈， n個Q的具有色素結構的重複單元的個數的平均值為兩個以上， n表示3～10的整數。In the present invention, the pigment polymer represented by the general formula (1) is preferably represented by the general formula (2). [Chem 2]

In the general formula (2), A ¹ represents an n-valent linking group, and B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -,- NROC- or -CONR-, R represents a hydrogen atom, an alkyl group or an aryl group, C ¹ represents a single bond or a divalent linking group, S represents a sulfur atom, and Q represents a polymer chain containing a repeating unit having a pigment structure, The average value of the number of n Q repeating units having a dye structure is two or more, and n represents an integer of 3-10.

In addition, the structure of the following formula (2a) other than Q in the general formula (2) corresponds to the linking group P in the general formula (1). * Indicates the bonding position with Q. [Chemical 3]

環、三伸苯環、茀環、聯苯環等，較佳為苯環。 雜環基較佳為5員環或6員環。雜環基可為單環，亦可為多環。作為雜環基中所含有的雜原子，可例示氮原子、氧原子、硫原子。較佳為氮原子。雜原子的數量較佳為1～3。作為雜環，例如可列舉三聚氰酸環、三嗪環、噁烷環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹噁唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、呫噸環、啡噁噻環、啡噻嗪環、啡嗪環，較佳為三聚氰酸環、三嗪環、噁烷環。 A¹ 所表示的n價的連結基可較佳地列舉主鏈上可具有氧原子的烴基、芳香族環基、雜環基、主鏈上可具有氧原子的烴基與芳香族環基的組合、主鏈上可具有氧原子的烴基與雜環基的組合等。 作為A¹ 為芳香族環基、雜環基、主鏈上可具有氧原子的烴基與芳香族環基的組合、或主鏈上可具有氧原子的烴基與雜環基的組合時的連結基P（所述式（2a）），例如可列舉以下者。 [化4]

式中，X表示主鏈上可具有氧原子的烴基， B¹ 表示單鍵、-O-、-S-、-CO-、-NR-、-O₂ C-、-CO₂ -、-NROC-、或-CONR-， R表示氫原子、烷基或芳基， C¹ 表示單鍵或二價的連結基， S表示硫原子， n表示3以上的整數。 *表示與Q的鍵結位置。In the general formula (2), A ¹ represents an n-valent linking group. The n-valent linking group is preferably a group containing one kind or a combination of two or more kinds selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain. Examples of the aliphatic hydrocarbon group include alkylene groups and alkenyl groups. The carbon number of the alkylene group is, for example, preferably 1 to 60, more preferably 1 to 30. The carbon number of the alkenyl group is, for example, preferably 1 to 60, more preferably 1 to 30. Examples of the aliphatic hydrocarbon group having an oxygen atom in the main chain include groups represented by -(OR ^x1 ) _m -and -(R ^x1 O) _m -. The aliphatic hydrocarbon group having an oxygen atom in the main chain may be any of linear, branched, and cyclic. In addition, the main chain refers to the skeleton portion of the linking group, and does not include a substituent. R ^x1 represents alkylene or alkenyl. m represents an integer of 1 or more, and when m is 2 or more, m R ^x1 may be the same or different. The carbon number of the alkylene group represented by R ^x1 is preferably 1-20, more preferably 1-10, and still more preferably 1-5. The alkylene group may be any of linear, branched, and cyclic. The carbon number of the alkenylene group represented by R ^x1 is preferably 2-20, more preferably 2-10, and still more preferably 2-5. The alkenylene group may be any of linear, branched, and cyclic. The aromatic ring group may be monocyclic or polycyclic. Examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring,

The ring, triphenylene ring, stilbene ring, biphenyl ring and the like are preferably benzene rings. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be monocyclic or polycyclic. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. It is preferably a nitrogen atom. The number of hetero atoms is preferably 1 to 3. Examples of the heterocyclic ring include cyanuric acid ring, triazine ring, oxane ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, Pyridazine ring, indazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoline Oxazoline ring, isoquinoline ring, carbazole ring, morphine ring, acridine ring, morpholine ring, thioanthracene ring, chromene ring, xanthene ring, phenoxazine ring, phenothiazine ring, phenothiazine ring, phenazine The ring is preferably a cyanuric acid ring, a triazine ring, or an oxane ring. The n-valent linking group represented by A ¹ is preferably a combination of a hydrocarbon group which may have an oxygen atom in the main chain, an aromatic ring group, a heterocyclic group, and a combination of a hydrocarbon group which may have an oxygen atom in the main chain and an aromatic ring group , Combination of hydrocarbon group and heterocyclic group which may have an oxygen atom in the main chain, etc. The linking group when A ¹ is an aromatic cyclic group, heterocyclic group, a combination of a hydrocarbon group having an oxygen atom in the main chain and an aromatic ring group, or a combination of a hydrocarbon group having an oxygen atom in the main chain and a heterocyclic group P (the formula (2a)) includes, for example, the following. [Chemical 4]

In the formula, X represents a hydrocarbon group that may have an oxygen atom in the main chain, B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC -, or -CONR-, R represents a hydrogen atom, an alkyl group or an aryl group, C ¹ represents a single bond or a divalent linking group, S represents a sulfur atom, and n represents an integer of 3 or more. * Indicates the bonding position with Q.

In the general formula (2), B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-. Preferably, it is a single bond, -O-, -CO-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-. R represents a hydrogen atom, an alkyl group or an aryl group. The carbon number of the alkyl group represented by R is preferably from 1 to 30, more preferably from 1 to 10. The alkyl group may be any of linear, branched, and cyclic. The carbon number of the aryl group represented by R is preferably 6-30, more preferably 6-12. R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

In the general formula (2), C ¹ represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, an aryl group, an oxyalkylene group, and more preferably an alkylene group or an oxyalkylene group. The carbon number of the alkylene group and the oxyalkylene group is preferably from 1 to 30, more preferably from 1 to 10. The alkyl group and the oxyalkylene group may be linear, branched, or cyclic. The carbon number of the arylene group is preferably 6-30, more preferably 6-12.

The following shows specific examples of the n-valent linking group represented by P. However, in the present invention, it is not limited by these specific examples.

[Chem 5]

[化6]

[化7]

The n-valent linking group is preferably the aforementioned (P-1) to (P-8), (P-16) to (P-20), and (P-22) to (P-32).

<<<polymer chain Q>>> The polymer chain represented by Q represents a polymer chain containing a repeating unit having a dye structure, and the average number of n Q repeating units having a dye structure is two or more . Regarding the n Qs contained in the general formula (1) or the general formula (2), each of the Q contains two or more repeating units having a pigment structure. The dye multimer represented by the general formula (1) or the general formula (2) contains 2n or more repeating units having a dye structure. The n Qs can be the same or different. The polymer chain represented by Q preferably has an average value of 2 to 20 repeating units having a pigment structure, more preferably 2 to 15 and even more preferably 2 to 10. The average value of the number of repeating units having a pigment structure can be obtained by Nuclear Magnetic Resonance (NMR). Specifically, for example, the number of repeating units in the general formula (1) is obtained from the ratio of the peak area ratio of the n-valent linking group represented by P and the repeating unit of the polymer chain Q. Next, by dividing this value by n, the number of repeating units in the polymer chain Q can be calculated. The weight average molecular weight of the polymer chain Q is preferably 1,000 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

The coloring matter structure of each repeating unit may have the same coloring matter structure or the same skeleton, but different coloring matter structures such as substituents and central metals may also have different coloring matter structures. In addition, when the dye structure has a cation and an anion, the cation and anion may be located in the same molecule as the dye structure of the polymer chain Q, or may be located outside the molecule of the dye structure. In addition, having a cation and an anion in the same molecule of the dye structure means that the cation and anion are bonded via a covalent bond. In addition, having an anion outside the molecule of the dye structure means that the cation and the anion do not bond via a covalent bond, but exist as other compounds. Hereinafter, the anions outside the molecule of the pigment structure are also referred to as counter anions.

The polymer chain represented by Q is not particularly limited as long as it contains a pigment structure, and is preferably one selected from (meth)acrylic resins, styrene resins, and (meth)acrylic/styrene resins . In addition, the (meth)acrylic resin refers to a resin containing (meth)acrylic resin as a main component. The inclusion of (meth)acrylic resin as the main component means that the (meth)acrylic resin preferably contains 50% by mass or more of (meth)acrylic resin, and more preferably contains 60% by mass or more. Preferably, it contains 70% by mass or more. In addition, the styrene-based resin refers to a resin containing styrene resin as a main component. The inclusion of styrene resin as a main component means that the styrene-based resin preferably contains 50% by mass or more of styrene resin, more preferably contains 60% by mass or more, and particularly preferably contains 70% by mass or more. In addition, the (meth)acrylic/styrene-based resin refers to a resin containing (meth)acrylic resin and styrene resin as main components. Containing (meth)acrylic resin and styrene resin as main components means that (meth)acrylic/styrene-based resin preferably contains 50% by mass or more of (meth)acrylic resin and styrene in total The resin preferably contains 60% by mass or more, and particularly preferably contains 70% by mass or more. Hereinafter, the polymer chain Q will be described in detail.

<<Framework structure of a repeating unit having a pigment structure>>>> As the frame structure of a repeating unit having a pigment structure, there is no particular limitation, and it is preferable to set paragraph number 0276 of Japanese Patent Laid-Open No. 2013-28764 to At least one of the structural units represented by general formula (A), general formula (B), and general formula (C) shown in paragraph number 0304 is used as a skeleton, or preferably represented by general formula (D) Pigment multimers. The description of paragraph number 0276 to paragraph number 0304 of Japanese Patent Laid-Open No. 2013-28764 can be incorporated into the specification of this application. In the present invention, it is preferable to contain a repeating unit represented by the following general formula (a1-1). In addition, the total of repeating units having a pigment structure in all repeating units constituting the polymer chain Q is preferably 5 mol% to 60 mol%, more preferably 10 mol% to 50 mol%, and still more preferably It is 20 mol% to 40 mol%.

[Chem 8]

In the general formula (a1-1), Q ¹ represents a trivalent linking group, L ¹ represents a single bond or a divalent linking group, D ¹ represents a dye structure, and “*” represents a binding bond to the main chain.

In the general formula (a1-1), Q ¹ represents a trivalent linking group. Q ¹ is a linking group formed by polymerization, and refers to a portion that forms a repeating unit corresponding to the main chain formed by polymerization. In addition, the parts indicated by the two "*" become repeating units. Q ¹ is not particularly limited as long as it is a linking group formed from a well-known polymerizable monomer, and it is particularly preferably a link represented by the following (XX-1) to the following (XX-24) The radical is more preferably a (meth)acrylic link chain represented by (XX-1) and (XX-2), a styrene link chain represented by (XX-10) to (XX-17), It is selected from vinyl chains represented by (XX-18), (XX-19), and (XX-24), preferably (A) represented by (XX-1) and (XX-2) Group) acrylic link chain, styrene link chain represented by (XX-10) to (XX-17), vinyl link chain represented by (XX-24), and more preferably (XX-1) and (XX-2) the (meth)acrylic-based connecting chain and the styrene-based connecting chain represented by (XX-11). (XX-1) to (XX-24) indicate that L ^{1 is} connected to the portion indicated by *. Me represents methyl. In addition, R in (XX-18) and (XX-19) represents a hydrogen atom, a C 1-5 alkyl group or a phenyl group.

[化10]

[化9]

[化10]

In the general formula (a1-1), L ¹ independently represents a single bond or a divalent linking group. As a divalent linking group, it represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (eg, methylene, ethylidene, trimethylene, propylidene, butylidene, etc.), carbon number 6-30 substituted or unsubstituted aryl aryl groups (such as phenyl phenyl, naphthyl, etc.), substituted or unsubstituted heterocyclic groups, -CH=CH-, -O-, -S- , -C(=O)-, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -, and these two or more Link base. In addition, L ¹ is preferably a structure containing anions. L ^{1 is more} preferably a single bond or an alkylene group, and further preferably a single bond or -(CH ₂ ) _n- (n is an integer of 1 to 5). Here, R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. D ¹ represents a dye structure derived from a dye compound described later.

<<<<Dye Structure>>>> The dye structure is not particularly limited, and various dye structures including known dye structures can be applied. For specific pigment compounds that can form pigment structures, in the "New Dyestuff Handbook" (Edited by the Society of Organic Synthetic Chemistry; Maruzen, 1970) and "Colour Index" (The Society of Dyers and colourists )), "Pigment Handbook" (edited by Ogawara et al.; Kodansha, 1986), etc. For example, a pigment structure derived from a pigment selected from quinone pigments (benzoquinone pigments, naphthoquinone pigments, anthraquinone pigments, anthrapyridone pigments, etc.), carbonium pigments (diarylmethane pigments, Triarylmethane pigments, xanthene pigments, acridine pigments, etc.), quinone imine pigments (oxazine pigments, thiazine pigments, etc.), azine pigments, polymethine pigments (oxacyanine pigments) , Cyanine pigments, arylene pigments, styrene pigments, cyanine pigments, squarylium salt pigments, ketonium pigments, etc.), quinophthalone pigments, phthalocyanine pigments, phthalocyanine pigments, purple rings Ketone pigments, indigo pigments, thioindigo pigments, quinoline pigments, nitro pigments, nitroso pigments, dipyrromethene pigments, azo pigments and these metal complex pigments. Among these dye structures, from the viewpoint of color separation and light resistance, it is preferably selected from triarylmethane dyes, xanthene dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, and quinophthalein The pigment structure of ketone pigment, phthalocyanine pigment, subphthalocyanine pigment, azo pigment and dipyrromethene pigment is more preferably selected from triarylmethane pigment, xanthene pigment, anthraquinone pigment, squarylium salt The pigment structure in the pigment, quinophthalone pigment, phthalocyanine pigment, subphthalocyanine pigment, azo pigment and dipyrromethene pigment is more preferably triarylmethane pigment or xanthene pigment. The pigment structure contained in the polymer chain represented by Q may be only one kind, or may be two or more kinds. Hereinafter, the dye structure that can be preferably used in the present invention will be specifically described.

<<<<<Triarylmethane dye>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from a triarylmethane dye (triarylmethane compound). Examples of the triarylmethane dye include compounds represented by the following formula (TP). The triarylmethane compound refers to a general term for a compound having a pigment structure containing a triarylmethane skeleton in the molecule.

Formula (TP) [Chem 11]

In the formula (TP), Rtp ¹ to Rtp ⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent a hydrogen atom, an alkyl group, or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent substituents. a, b and c represent integers from 0 to 4. When a, b and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be linked to each other to form a ring. X ^- represents an anionic structure. When X ^- is not present, at least one of Rtp ¹ to Rtp ⁷ contains an anion.

Rtp ¹ to Rtp ^{6 are} preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp ^{5 is} preferably a hydrogen atom or NRtp ⁹ Rtp ¹⁰ , particularly preferably NRtp ⁹ Rtp ¹⁰ . Rtp ⁹ and Rtp ^{10 are} preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or a phenyl group. As the substituents represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ , the substituents listed in the section of Substituent Group A described later can be used. In particular, a straight-chain or branched alkyl group having 1 to 5 carbon atoms is preferred. C1-C5 alkenyl group, C6-C15 aryl group, carboxyl group or sulfo group, more preferably C1-C5 linear or branched alkyl group, C1-C5 alkenyl group, benzene Group or carboxyl group. In particular, Rtp ⁶ and Rtp ^{8 are} preferably an alkyl group having 1 to 5 carbon atoms, and Rtp ^{7 is} preferably an alkenyl group (particularly preferably a phenyl group formed by connecting two adjacent alkenyl groups), a phenyl group, or a carboxyl group. a, b, or c each independently represent an integer of 0 to 4. In particular, a and b are preferably 0 to 1, and c is preferably an integer of 0 to 2.

通式（P）中，L表示單鍵或二價的連結基，X¹ 自選自-SO₃ ^- 、-COO^- 、-PO₄ ^- 、含有由下述通式（A1）所表示的結構的基及含有由下述通式（A2）所表示的結構的基中的至少一種中選擇。 通式（A1） [化13]

通式（A1）中，R¹ 及R² 分別獨立地表示-SO₂ -或-CO-。 通式（A2） [化14]

通式（A2）中，R³ 表示-SO₂ -或-CO-。R⁴ 及R⁵ 分別獨立地表示-SO₂ -、-CO-或-CN。When at least one of Rtp ¹ to Rtp ⁷ contains an anion, examples of the anion include at least one structure of Rtp ¹ to Rtp ⁷ substituted with the general formula (P). General formula (P) [Chem. 12]

In the general formula (P), L represents a single bond or a divalent linking group, X ¹ managed from _{^{-SO 3 -, -COO -, -PO}} 4 -, structure represented by the following general formula (A1) represented contained At least one of a group and a group containing a structure represented by the following general formula (A2) is selected. General formula (A1) [Chem. 13]

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-. General formula (A2) [Chem. 14]

In the general formula (A2), R ³ represents -SO ₂ -or -CO-. R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO-, or -CN.

In the general formula (P), L represents a single bond or a divalent linking group. The divalent linking group preferably represents a group that represents -NR ¹⁰ -, -O-, -SO ₂ -, a fluorine-substituted alkylene group, a fluorine-substituted alkylene group, or a combination including these. In particular, it is preferably a group containing a combination of -NR ¹⁰ -and -SO ₂ -and a fluorine-substituted alkylene group, a group containing a combination of -O- and a fluorine-substituted phenylene group, or containing -NR ¹⁰ -and -SO ₂ -and a fluorine-substituted phenylene group. In -NR ¹⁰ -, R ¹⁰ represents a hydrogen atom or a C 1-5 alkyl group, preferably a hydrogen atom. The carbon number of the fluorine-substituted alkylene group is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of fluorine-substituted alkylene include difluoromethylene, tetrafluoroethyl, hexafluoropropyl, and the like. The carbon number of the fluorine-substituted phenylene group is preferably 6-20, more preferably 6-14, and even more preferably 6-10. Specific examples of the fluorine-substituted phenylene group include tetrafluorophenylene group, hexafluoro-1-naphthyl group, and hexafluoro-2-naphthyl group.

In the general formula (P), X ¹ is an anion, preferably managed from -SO ₃ ^-, -COO ^-, contains a group represented by the formula (A1) and a structure represented by the general formula comprising (A2) represented by Choose from at least one of the bases of the structure. Group preferably contains a structure represented by the general formula (A1) is represented by said general formula (A1), at the end one of R ¹ and R ² having fluorine-substituted alkyl group, more preferably R ¹ and R ² One of them directly bonds with the fluorine-substituted alkyl group. The carbon number of the fluorine-substituted alkyl group is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 1 to 3, still more preferably from 1 or 2, and particularly preferably from 1. These alkyl groups are more preferably perfluoroalkyl groups. As a specific example of the fluorine-substituted alkyl group, trifluoromethyl is preferred. The group containing the structure represented by the general formula (A2) is preferably the above-mentioned general formula (A2), having a fluorine-substituted alkyl group at the end of at least any one of R ³ to R ⁵ , more preferably R ³ to At least two of R ⁵ are directly bonded to the fluorine-substituted alkyl group. In particular, preferred alkyl is substituted at the end of at least two of R ³ ~ R ⁵ is a fluorine, more preferably at least two direct-fluoro-R ³ ~ R ⁵ is a substituted alkyl group bonded performed. The meaning of the fluorine-substituted alkyl group is the same as that explained for the group containing the structure represented by the general formula (A1), and the preferred range is also the same.

<<<<<xanthene dye>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from xanthene dye (xanthene compound). Examples of the xanthene dye include xanthene compounds represented by the following formula (J).

通式（J）[化15]

General formula (J)

In formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m represents an integer of 0 to 5. X ^- represents a counter anion. When X ^- is not present, at least one of R ⁸¹ to R ⁸⁵ contains an anion.

The substituents that can be used for R ⁸¹ to R ⁸⁵ in formula (J) are the same as the substituents listed in the section of substituent group A described later. In formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more may be independently bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring, or Unsaturated ring with 5, 6 or 7 members. When the formed 5-membered, 6-membered, or 7-membered ring is a group that can be further substituted, it can also be substituted with the substituents described in R ⁸¹ to R ⁸⁵ , and when substituted with two or more substituents, these The substituents may be the same or different. When R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and m is 2 or more in the formula (J), R ^{85 is} independently bonded to each other to form a 5-membered, 6-membered and 7-membered saturated ring, or 5-membered, 6-membered and 7-membered unsaturated ring, as 5-membered, 6-membered and 7-membered saturated rings without substituents, or 5-membered, 6-membered and 7-membered unsaturated rings Saturated rings include, for example, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring , Benzene ring, pyridine ring, pyrazine ring, pyridazine ring, preferably benzene ring, pyridine ring. Examples of the anions include those mentioned above.

In particular, R ⁸² and R ⁸³ are preferably hydrogen atoms or substituted or unsubstituted alkyl groups, and R ⁸¹ and R ⁸⁴ are substituted or unsubstituted alkyl groups or phenyl groups. In addition, R ^{85 is} preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, an amide group, more preferably a sulfo group, a sulfonamide group, a carboxyl group , Amidyl. R ^{85 is} preferably bonded to the adjacent portion of the carbon connected to the xanthene ring. The substituents possessed by the phenyl group of R ⁸¹ and R ⁸⁴ are particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.

The compound having a xanthene skeleton represented by formula (J) can be synthesized by a method described in the literature. Specifically, "Tetahedron Letters", 2003, vol. 44, No. 23, pages 4355 to 4360; "Tetahedron", 2005, vol. 61, The method described in No. 12, pages 3097 to 3106, etc.

When X ^- represents an anion, refer to the description below when the counter anion is a different molecule. In addition, when X ^{− is} not present, and at least one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ contains an anion, the description can be referred to when the counter anion is in the same constituent unit.

In addition, in the dye structure, the cations are not localized, and therefore exist on a nitrogen atom or a carbon atom of a xanthene ring as shown below, for example. [Chem 16]

<<<<<Anthraquinone Dye>>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from an anthraquinone dye. As the anthraquinone dye (anthraquinone compound), a compound represented by the following general formula (AQ-1) to general formula (AQ-3) is preferable. The anthraquinone compound refers to a general term for a compound having a pigment portion containing an anthraquinone skeleton in the molecule.

[化17]

In the general formula (AQ-1), A and B each independently represent an amine group, a hydroxyl group, an alkoxy group, or a hydrogen atom. Xqa represents ORqa ¹ or NRqa ² Rqa ³ . Rqa ¹ to Rqa ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rq ₁ to Rq ₄ represent a substituent. The substituents that can be used for Rq ₁ to Rq ₄ are the same as the substituents listed in the section of substituent group A described later. Ra and Rb each independently represent a hydrogen atom, an alkyl group or an aryl group.

In the general formula (AQ-2), C and D have the same meaning as A and B in the general formula (AQ-1). Xqb represents ORqb ¹ or NRqb ² Rqb ³ . Rqb ¹ to Rqb ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rq ₅ to Rq ₈ represent a substituent. Rq ₅ to Rq _{8 have} the same meaning as Rq ₁ to Rq ₄ in the general formula (AQ-1). The meaning of Rc is the same as Ra or Rb in the general formula (AQ-1).

In the general formula (AQ-3), E and F have the same meaning as A and B in the general formula (AQ-1). Xqc represents ORqc ¹ or NRqc ² Rqc ³ . Rqc ¹ to Rqc ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rq ₉ to Rq _{12 have} the same meaning as Rq ₁ to Rq ₄ in the general formula (AQ-1). The meaning of Rd is the same as Ra or Rb in the general formula (AQ-1). For preferred ranges of the general formula (AQ-1), the general formula (AQ-2) and the general formula (AQ-3), for example, refer to paragraph 0045 to paragraph 0047 of Japanese Patent Laid-Open No. 2013-29760, which The content can be incorporated into the specification of this application.

As the anthraquinone pigment, for example, reference can be made to paragraphs 0049 to 0050 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application.

<<<<<Cyanine Pigment>>>>> The preferred form of the pigment structure in the present invention is one having a partial structure derived from cyanine pigment (cyanine compound). As the cyanine pigment, a compound (cyanine compound) represented by the following general formula (PM) is preferable. In the present invention, the cyanine compound refers to a compound having a pigment portion containing a cyanine skeleton in the molecule.

通式（PM）[Chemical 18]

General formula (PM)

In the general formula (PM), ring Z1 and ring Z2 each independently represent a heterocyclic ring which may have a substituent. l represents an integer from 0 to 3. X ^- represents an anion. As a preferable range of the general formula (PM), for example, reference can be made to paragraphs 0077 to 0008 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application. In addition, in the specific examples of the cyanine pigment described in paragraphs 0077 to 0008 of Japanese Patent Laid-Open No. 2013-29760, any hydrogen atom in the structure of the cyanine pigment and R ^{2 in the} general formula (1) Perform bonding.

<<<<<squarylium squarylium salt dye>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from squarylium sialium salt dye (squarylium squarium salt compound). As the squarylium salt dye, a compound (squarylium salt compound) represented by the following general formula (K) is preferred. In the present invention, the squarylium salt compound refers to a general term for a compound having a dye portion containing a squarylium salt skeleton in the molecule.

通式（K）[Chem 19]

General formula (K)

In the general formula (K), A and B each independently represent an aryl group or a heterocyclic group. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group is preferably a five-membered ring or a six-membered ring heterocyclic group, and examples thereof include pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, triazol-1-yl, Thienyl, furanyl, thiadiazolyl, etc. As a preferable range of the general formula (K), for example, reference can be made to paragraphs 0088 to 0106 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application. As a specific example of the squarylium onium salt dye, for example, refer to paragraph 0105 of Japanese Patent Laid-Open No. 2013-29760.

<<<<<Quinophthalone Dye>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from a quinophthalone dye (quinophthalone compound). The quinophthalone pigment is preferably a compound (quinophthalone compound) represented by the following general formula (QP). In the present invention, the quinophthalone compound refers to a general term for a compound having a pigment portion containing a quinophthalone skeleton in the molecule.

通式（QP）[化20]

General formula (QP)

In the general formula (QP), Rqp ₁ to Rqp ₆ each independently represent a hydrogen atom or a substituent. When at least two of Rqp ₁ to Rqp ₆ are in adjacent positions, they may be bonded to each other to form a ring, and the ring formed above may further have a substituent. As a preferable range of the general formula (QP), for example, reference can be made to paragraph 0110 to paragraph 0114 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application. As a specific example of the quinophthalone pigment, for example, refer to the description of paragraph 0113 of Japanese Patent Laid-Open No. 2013-29760.

<<<<<Phthalocyanine Dye>>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from a phthalocyanine dye (phthalocyanine compound). As the phthalocyanine dye, those having a partial structure derived from a compound (phthalocyanine compound) represented by the following general formula (F) are preferred. In the present invention, the phthalocyanine compound refers to a general term for a compound having a pigment portion containing a phthalocyanine skeleton in the molecule.

[化21]

In the general formula (F), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent 6 members composed of atoms selected from a hydrogen atom, a carbon atom, and a nitrogen atom Group of atoms required for the ring. As a preferable range of the general formula (F), for example, reference can be made to paragraphs 0118 to 0124 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application. As a specific example of the phthalocyanine dye, for example, refer to paragraph 0123 of Japanese Patent Laid-Open No. 2013-29760.

<<<<<Phthalocyanine Dye>>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from a subphthalocyanine dye (subphthalocyanine compound). As the subphthalocyanine dye, a compound (subphthalocyanine compound) represented by the following general formula (SP) is preferable. In the present invention, the subphthalocyanine compound refers to a general term for a compound having a dye portion containing a subphthalocyanine skeleton in the molecule.

通式（SP）[化22]

General formula (SP)

In the general formula (SP), Z ¹ to Z ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amine group, an alkoxy group, an aryloxy group, and a thioether group. X represents an anion. As a preferable range of the general formula (SP), for example, reference can be made to paragraphs 0128 to 0133 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application. As a specific example of the subphthalocyanine dye, for example, refer to the description of paragraph 0132 of Japanese Patent Laid-Open No. 2013-29760.

<<<<<Azo Dyes>>>>> The preferred form of the dye structure in the present invention is one having a partial structure derived from an azo dye (azo compound). In the present invention, the term "azo compound" refers to a general term for a compound having a pigment site containing an N=N group in the molecule. As the azo dye, a known azo dye (for example, substituted azobenzene, etc.) can be appropriately selected and applied. For example, as an azo dye, reference may be made to the descriptions of paragraphs 0084 to 0134 of Japanese Patent Laid-Open No. 2013-41097 and the descriptions of paragraphs 0029 to 0136 of Japanese Patent Laid-Open No. 2011-162760, the contents of which can be Incorporated into this manual.

<<<<<Dipyrromethene Dye>>>> One of the forms of the dye structure of the present invention is one having a partial structure derived from a dipyrromethene dye. The dipyrromethene dye is preferably a dipyrromethene compound and a dipyrromethene metal complex compound obtained from the dipyrromethene compound and the metal or metal compound. For example, as the dipyrromethene dye, reference may be made to paragraphs 0033 to 0136 of Japanese Patent Laid-Open No. 2011-95732, and the contents thereof can be incorporated into the specification of the present application.

The pigment structure may also be substituted with a hydrogen atom in the pigment structure by a substituent selected from the following substituent group A. (Substituent group A) Examples of substituents that the dye structure may have include halogen atoms (for example, fluorine atoms, chlorine atoms, and bromine atoms), alkyl groups (preferably straight-chain and branched chains having 1 to 48 carbon atoms) , Or a cyclic alkyl group, more preferably a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl (preferably Tertiary butyl), pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1- Adamantyl), alkenyl (preferably alkenyl having 2 to 48 carbon atoms, more preferably alkenyl having 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), Alkynyl (preferably C 2-20, more preferably C 2-12, particularly C 2-8, for example, propargyl, 3-pentynyl, etc.), aryl (preferably It is an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as phenyl and naphthyl groups, and a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably Heterocyclic groups having 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1- Pyrazolyl, benzotriazol-1-yl), silane group (preferably silane group having 3 to 38 carbon atoms, more preferably silane group having 3 to 18 carbon atoms, such as trimethylsilyl group, triethyl group Silane group, tributyl silane group, third butyl dimethyl silane group, third hexyl dimethyl silane group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably carbon number 1 to 48 The alkoxy group is more preferably an alkoxy group having 1 to 24 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, third butoxy, Dodecyloxy, cycloalkoxy, such as cyclopentyloxy, cyclohexyloxy), aryloxy (preferably aryloxy having 6 to 48 carbon atoms, more preferably aryl having 6 to 24 carbon atoms) Oxygen group, such as phenoxy group, 1-naphthyloxy group, heterocyclic oxy group (preferably heterocyclic oxy group having 1 to 32 carbon atoms, more preferably heterocyclic oxy group having 1 to 18 carbon atoms, for example 1 -Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silaneoxy (preferably silaneoxy having 1 to 32 carbon atoms, more preferably silaneoxy having 1 to 18 carbon atoms , Such as trimethylsilyloxy, third butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy (preferably C2-48 acyloxy, more preferably Acyloxy having 2 to 24 carbon atoms, such as acetyloxy, trimethylethoxy, benzoyloxy, dodecyloxy), alkoxycarbonyloxy (preferably carbon 2 The alkoxycarbonyloxy group of -48 is more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, ethoxycarbonyloxy group, third butoxycarbonyloxy group, cycloalkoxycarbonyloxy group , For example, cyclohexyloxycarbonyloxy, aryloxycarbonyloxy (preferably aryloxycarbonyloxy having 7 to 32 carbon atoms, more preferably aryloxycarbonyloxy having 7 to 24 carbon atoms, Such as phenoxycarbonyloxy),

Carbamoyloxy group (preferably carbamoyloxy group having 1 to 48 carbon atoms, more preferably carbamoyloxy group having 1 to 24 carbon atoms, such as N,N-dimethylamine methoxyl group, N-butylamine carboxamide, N-phenylamine carboxyloxy, N-ethyl-N-phenylamine carboxyloxy), sulfamoyloxy (preferably carbon number 1 ~ 32 Sulfamoyloxy, preferably sulfamoyloxy having 1 to 24 carbon atoms, such as N,N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonate Acyloxy (preferably C1-C38 alkylsulfonyloxy, more preferably C1-C24 alkylsulfonyloxy, such as methylsulfonyloxy, hexadecylsulfonyloxy Group, cyclohexylsulfonyloxy group), arylsulfonyloxy group (preferably C6-32 arylsulfonyloxy group, more preferably C6-C24 arylsulfonyloxy group, for example Phenylsulfonyloxy), acyl (preferably acyl with 1 to 48 carbons, more preferably acyl with 1 to 24 carbons, such as methyl acetyl, ethyl acetyl, trimethyl ethyl acetyl , Benzoyl, tetradecyl, cyclohexyl), alkoxycarbonyl (preferably alkoxycarbonyl having 2 to 48 carbon atoms, more preferably alkoxycarbonyl having 2 to 24 carbon atoms, Eg methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl (Preferably an aryloxycarbonyl group having a carbon number of 7 to 32, more preferably an aryloxycarbonyl group having a carbon number of 7 to 24, such as a phenoxycarbonyl group), a carbamoyl group (preferably a carbon number of 1 to 48) Carboxamide, more preferably C 1-24, such as carboxamide, N,N-diethylamine carboxamide, N-ethyl-N-octylamine carboxamide , N,N-dibutylamine carboxamide, N-propylamine carboxamide, N-phenylamine carboxamide, N-methyl-N-phenylamine carboxamide, N,N-di Cyclohexylamine formamide), amine group (preferably an amine group having a carbon number of 32 or less, more preferably an amine group having a carbon number of 24 or less, such as an amine group, methylamino group, N,N-dibutylamine Group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group), aniline group (preferably an aniline group having 6 to 32 carbon atoms, more preferably an aniline group having 6 to 24, such as an aniline group , N-methylanilinyl group), heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably a heterocyclic amino group having 1 to 18, such as 4-pyridylamino group), carbon Acylamino group (preferably a carbon amide group having 2 to 48 carbon atoms, more preferably a carbon amide group having 2 to 24, such as an acetamide group, a benzamide group, a tetradecyl amide group, a triamide Methyl acetoyl amide group, cyclohexane amide group), urea group (preferably a urea group having 1 to 32 carbon atoms, more preferably a urea group having 1 to 24 carbon atoms, such as urea group, N, N-dimethylureido group, N-phenylureido group), imidate group (preferably imidate group having 36 or less carbon atoms, more preferably imidate group having 24 or less carbon atoms, such as N- Succinimide group, N-phthalimide group), alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms Alkoxycarbonylamino group, such as methoxycarbonylamino group, ethoxycarbonylamino group, first Tributoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino),

Aryloxycarbonylamino group (preferably aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably aryloxycarbonylamino group having 7 to 24 carbon atoms, such as phenoxycarbonylamino group), sulfonamide Amino group (preferably sulfonamide group having 1 to 48 carbon atoms, more preferably sulfonamide group having 1 to 24 carbon atoms, such as methanesulfonamide group, butane sulfonamide group, benzenesulfonamide group , Hexadecane sulfonamide, cyclohexane sulfonamide), sulfamoyl amine (preferably sulfamoylamino with 1 to 48 carbon atoms, more preferably 1 to 24 carbon) Amine sulfonamide, such as N,N-dipropyl sulfa amide, N-ethyl-N-dodecyl sulfa amide, azo (preferably carbon number 1 The azo group of -32 is more preferably an azo group having 1 to 24 carbon atoms, for example, phenylazo group and 3-pyrazolyl azo group, and an alkylthio group (preferably having 1 to 48 carbon atoms) The alkylthio group is more preferably an alkylthio group having 1 to 24 carbon atoms, such as methylthio group, ethylthio group, octylthio group, and cyclohexylthio group, and an arylthio group (preferably an aromatic group having 6 to 48 carbon atoms) The thio group is more preferably an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, and more preferably 1 to 18 carbon atoms) Heterocyclic thio group, such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), alkylsulfinyl (preferably C1-32 alkylsulfinyl Acyl group, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecylsulfinyl group), arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms) Group, more preferably an arylsulfinyl group having 6 to 24 carbon atoms, such as phenylsulfinyl group, and an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably C1-C24 alkylsulfonyl, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexyl Sulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl (preferably C6-48 arylsulfonyl, more preferably carbon 6-24 arylsulfonyl groups, such as phenylsulfonyl group, 1-naphthylsulfonyl group, sulfamoyl group (preferably sulfamoyl group having 32 or less carbon atoms, more preferably 24 carbon number The following sulfamoyl groups, such as sulfamoyl, N,N-dipropyl sulfamoyl, N-ethyl-N-dodecyl sulfamoyl, N-ethyl-N-phenylamine Sulfonyl group, N-cyclohexylamine sulfonyl group), sulfo group, phosphinyl group (preferably a phosphinyl group having 1 to 32 carbon atoms, more preferably a phosphinyl group having 1 to 24 carbon atoms, such as phenoxy Phosphinyl acetyl group, octyloxy phosphinyl group, phenyl phosphinyl group), phosphinyl amide group (preferably phosphinyl amide group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms Phosphinylamide group, such as diethoxyphosphinylamide group, dioctyloxyphosphinylamide group), alkoxycarbonyloxy group (preferably C5-30 alkoxy group The carbonylcarbonyloxy group is more preferably an alkoxycarbonyloxy group having 5 to 10 carbon atoms). These substituents may be further substituted. In addition, when there are two or more substituents, they may be the same or different. In addition, when possible, they may be connected to each other to form a ring. For details, refer to, for example, paragraphs 0027 to 0038 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application.

<<<<Counter Anion>>>> When the dye structure includes a cation and a counter anion, the counter anion is not particularly limited, but from the viewpoint of heat resistance, a non-nucleophilic anion is preferred. The non-nucleophilic counter anion is preferably a known non-nucleophilic anion described in paragraph No. 0075 of Japanese Patent Laid-Open No. 2007-310315. Here, the term "non-nucleophilic" refers to the property that the dye does not undergo nucleophilic attack due to heating. The counter anion is preferably selected from the group consisting of sulfonate anion, carboxylate anion, sulfonyl amide imide anion, bis(alkyl sulfonyl) amide imide anion, and tri(alkyl sulfonyl) methide anion , carboxylate anion, tetra aryl borate ^{anion, -CON - CO -, - CON} - SO 2 -, BF 4 -, PF 6 -, SbF 6 -, B - (CN) 3 OCH 3 is at least one. More preferably, it is selected from sulfonate anion, sulfonyl amide imide anion, bis(alkyl sulfonyl) amide imide anion, tri(alkyl sulfonyl) methide anion, carboxylate anion, tetraaryl borate _{^{anion, BF 4 -, PF 6 -}} , and SbF ₆ ^- in at least one. Among these, as the counter anion, a non-nucleophilic anion having a structure represented by the following (AN-1) to (AN-5) is more preferable.

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In formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² may be bonded to each other to form a ring. X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom, preferably a fluorine atom or a C 1-10 alkyl group having a fluorine atom, more preferably a carbon number 1 A perfluoroalkyl group of -10, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a trifluoromethyl group.

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In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ³ , X ⁴ and X ⁵ are independent, and have the same meanings as X ¹ and X ² , and the meanings of the preferred ranges are also the same.

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In the formula (AN-3), X ⁶ represents a C 1-10 alkyl group having a fluorine atom. X ^{6 is} preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. [化26]

In the formula (AN-4), X ⁷ represents a C 1-10 alkylene group having a fluorine atom. X ^{7 is} preferably a perfluoroalkylene group having 1 to 10 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 4 carbon atoms.

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In formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms base. The aryl groups represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. When it has a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group, etc. are mentioned, Preferably a halogen atom and The alkyl group is more preferably a fluorine atom or an alkyl group, and still more preferably a fluorine atom or a C 1-4 perfluoroalkyl group. Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are more} preferably phenyl groups each independently having a halogen atom and/or an alkyl group containing a halogen atom, and still more preferably an alkyl group having a fluorine atom and/or a fluorine atom Phenyl.

In addition, the non-nucleophilic counter anion is preferably -B(CN) _n1 (OR ^a ) _4-n1 (R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents 1 ~ 4 integer). ^Ra as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. ^Ra as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group. n1 is preferably 1 to 3, more preferably 1 to 2.

Further, non-nucleophilic counter anion is preferably ^{_{-PF 6 R P (6-n2}} ) - (R P represents a fluorinated alkyl group having a carbon number of 1 to 10, n2 represents an integer of 1 to 6). R ^{P is} preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably an alkyl group having a fluorine atom having 1 to 4 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. n2 is preferably an integer of 1 to 4, more preferably 1 or 2.

The mass per molecule of the non-nucleophilic counter anion is preferably 100 to 1,000, and more preferably 200 to 500. The pigment polymer (A) may contain only one kind of non-nucleophilic counter anion, or two or more kinds. Hereinafter, specific examples of non-nucleophilic counter anions are shown, but the present invention is not limited thereto.

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[Chem 29]

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The following shows specific examples of the repeating unit having a pigment structure that can be suitably used in the present invention. Of course, the present invention is not limited to these specific examples.

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<<<<Other Repeating Units>>>> In addition to the repeating unit having a dye structure, the polymer chain Q may contain other repeating units. Other repeating units may contain functional groups such as polymerizable groups and acid groups. It may not contain functional groups. It is preferable to contain one or more types selected from the repeating unit having an acid group and the repeating unit having a polymerizable group, and it is more preferable to contain a repeating unit having an acid group.

As the polymerizable group, a known polymerizable group that can be cross-linked by radicals, acids, or heat can be used, and examples thereof include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxa Cyclobutyl), hydroxymethyl and the like are preferably a group containing an ethylenically unsaturated bond, and more preferably a (meth)acryloyl group. The (meth)acryloyl group may be introduced by reacting glycidyl (meth)acrylate with 3,4-epoxy-cyclohexylmethyl (meth)acrylate. When the polymer chain Q contains a repeating unit having a polymerizable group, the ratio of the repeating unit having a polymerizable group to 100 moles of all repeating units of the polymer chain Q is preferably, for example, 5 to 50 moles. More preferably, it is 10 mol to 40 mol.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acid group may contain only one kind or two or more kinds. When the polymer chain Q contains a repeating unit having an acid group, the ratio of the repeating unit having an acid group is preferably, for example, 5 mol to 50 mol with respect to 100 mol of all the repeating units of the polymer chain Q. It is 10 mol to 40 mol.

Examples of other functional groups include groups containing 2 to 20 unsubstituted repeating alkoxy chains, lactone groups, acid anhydride groups, amide groups, cyano groups, and other development promoting groups, long-chain alkyl groups and Hydrophilicity-adjusting groups such as cyclic alkyl groups, aralkyl groups, aryl groups, polyoxyalkylene groups, hydroxyl groups, maleimide groups, amine groups, etc., can be suitably introduced. In a group containing 2 to 20 unsubstituted repeating alkoxylated chains, the number of repeating alkoxylated chains is preferably 2 to 10, more preferably 2 to 15, and even more 2 to 10 are preferred. One alkoxy chain is represented by -(CH ₂ ) _n O-, n is an integer, n is preferably 1-10, more preferably 1-5, and even more preferably 2 or 3.

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Specific examples of other repeating units are shown, but the invention is not limited thereto. [化35]

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«<< Polymer chain not containing a dye structure>>> The dye multimer (A) may have a polymer chain not containing a dye structure. Examples of polymer chains that do not contain a pigment structure include polymer chains including the repeating units described in the other repeating units of the polymer chain Q.

<<Various properties of the dye polymer (A)>> The weight average molecular weight of the dye polymer (A) is preferably 1,000 to 100,000. For example, the lower limit is more preferably 3000 or more, further preferably 4000 or more, and still more preferably 5000 or more. The upper limit is more preferably 50,000 or less, more preferably 20,000 or less, and still more preferably 15,000 or less. If the weight-average molecular weight is within the above range, the color shiftability is better. Furthermore, the developability is improved, and the generation of developing residue can be further reduced.

The acid value of the pigment polymer (A) is preferably 10 mgKOH/g or more. The lower limit is more preferably 15 mgKOH/g or more, and further preferably 20 mgKOH/g or more. The upper limit is more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less. If the acid value is 10 mgKOH/g or more, the developability is improved, and the generation of developing residue can be further reduced.

The method for measuring the specific absorbance of the dye polymer (A) includes, for example, the following methods: using a solvent having sufficient solubility for the dye polymer (A), the maximum absorbance in 400 nm to 800 nm becomes 1.0 Adjust the concentration of the solution containing the pigment polymer (A), and measure the absorbance of the solution at 25°C using a unit with an optical path length of 1 cm. The solvent used when measuring the specific absorbance can be suitably used as long as it has sufficient solubility for the pigment polymer (A). Preferred solvents include tetrahydrofuran, methanol, isopropanol, dimethyl sulfoxide, acetonitrile, ethyl acetate, hexane, toluene, water, concentrated sulfuric acid, methanesulfonic acid and the like. Tetrahydrofuran is used when tetrahydrofuran has sufficient solubility. Among the maximum absorption wavelengths within 400 nm to 800 nm, the specific absorbance represented by the following formula (Aλ) is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and particularly preferably 30 or more. If the specific absorbance is 5 or more, it can be suitably used as a colorant. E=A/(c×l)... (Aλ) In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength within 400 nm to 800 nm, and A represents the maximum absorption within 400 nm to 800 nm The absorbance at the absorption wavelength, l represents the unit length expressed in cm, and c represents the concentration of the pigment polymer in the solution expressed in mg/ml.

The pigment polymer (A) is preferably a dye. The dye refers to a dye having substantial solubility in water or an organic solvent, particularly preferably an organic solvent-soluble dye dissolved in the following organic solvent. Examples of organic solvents include esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, etc.), Ethers (such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), for these organic solvents, it is preferable to dissolve 1% by mass to 50% by mass, more preferably dissolve by 5% by mass ~40% by mass, particularly preferably 10% to 30% by mass. By being within this range, when the coloring composition of the present invention is applied to the production of a color filter or the like, the coating surface shape becomes suitable, and further, it can be further reduced by the elution after coating other colors The concentration drops.

In the coloring composition of the present invention, one kind of pigment polymer (A) may be used alone, or two or more kinds may be used in combination.

The content of the pigment polymer (A) in the coloring composition of the present invention is set in consideration of the content ratio with other pigments (preferably pigments) and the like described later. The mass ratio of the pigmented polymer to the pigment (pigmented polymer (A)/pigment) is preferably 0.1 to 5, more preferably 0.2 to 2, and even more preferably 0.3 to 1. The content of the pigment polymer (A) in the coloring composition of the present invention is preferably 1.0% by mass to 50% by mass, more preferably 5.0% by mass to 30% by mass relative to the total solid content in the coloring composition. Particularly good is 10% by mass to 25% by mass.

<<Synthesis method of dye polymer (A)>> The production method of the dye polymer represented by the general formula (1) is not particularly limited, but it can be 3 to 10 per molecule A multifunctional thiol compound of each thiol group and a compound having a dye structure and a radical polymerizable group are produced by radical polymerization. Hereinafter, the compound having a dye structure and a radical polymerizable group is also referred to as a "radical polymerizable dye compound". Among the radically polymerizable dye compounds, as the dye structure, the above-mentioned ones can be mentioned. In the radically polymerizable dye compound, examples of the radically polymerizable group include a group containing an ethylenically unsaturated bond such as a vinyl group, (meth)allyl group, and (meth)acryloyl group. More specifically, a method of radically polymerizing the compound represented by the general formula (3) and a radically polymerizable dye compound is preferable. P ⁰ -(SH) _n (3) In the general formula (3), P ⁰ represents an n-valent linking group, SH represents a thiol group, and n represents an integer of 3-10.

In the general formula (3), P ⁰ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur The atomic group may be unsubstituted or may further have a substituent. The n-valent linking group represented by P ⁰ preferably contains 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to Base of 10 sulfur atoms. More preferably, it is a group containing 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms. Even more preferably, it is a group containing 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms. The n-valent linking group represented by P ⁰ is preferably a linking group derived from a polyol. The compound represented by the general formula (3) is preferably a compound represented by the general formula (4). A ⁰ -(B ⁰ -C ⁰ -SH) _n (4) In the general formula (4), A ⁰ represents an n-valent linking group, and B ⁰ represents a single bond, -O-, -S-,- CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-, R represents a hydrogen atom, an alkyl group or an aryl group, C ⁰ represents a single bond or a divalent linking group, SH represents a thiol group, and n represents an integer of 3-10. The meanings of A ⁰ , B ⁰ and C ⁰ in the general formula (4) are the same as the ranges described for A ¹ , B ¹ and C ¹ in the general formula (2), and the preferred forms are also the same. As specific examples of the compound represented by the general formula (3), the following compounds may be mentioned.

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Among the above, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, particularly preferred compounds are preferably (SH-1) to (SH-8), (SH-16 ) ~ (SH-20), (SH-22) ~ (SH-32).

The radical polymerization of the polyfunctional thiol compound and the radically polymerizable dye compound can be obtained, for example, by a method in which the polyfunctional thiol compound and the radically polymerizable dye compound are dissolved in an appropriate solvent, and freely added thereto The base generating agent is then added at a temperature of about 50°C to 100°C (thiol-ene reaction method).

As an example of a suitable solvent used in the thiol-ene reaction method, it can be arbitrarily selected according to the solubility of the polyfunctional thiol compound and the radical polymerizable dye compound. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl Isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. These solvents can also be used in combination of two or more.

In addition, as a free radical generator, such as 2,2'-azobis (isobutyronitrile) (Azobisisobutyronitrile, AIBN), 2,2'-azobis-(2,4'-dimethylvaleronitrile) ), 2,2'-azobisisobutyric acid like azo compounds, such as peroxides like benzoyl peroxide, and persulfates like potassium persulfate and ammonium persulfate.

<<Polymerizable compound>> The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound that can be cross-linked by free radicals, acid, or heat can be used. For example, a compound containing a group having an ethylenic unsaturated bond, a cyclic ether (epoxy group, oxetane) group, methylol group, etc. may be mentioned. Examples of the group having an ethylenic unsaturated bond include a vinyl group, (meth)allyl group, (meth)acryloyl group and the like. In the present invention, the polymerizable compound is preferably a trifunctional to hexafunctional (meth)acrylate compound. The polymerizable compound may be, for example, any one of chemical forms such as monomers, prepolymers (that is, dimers, trimers, and oligomers), mixtures of these, and polymers of these.

Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides , And these polymers, preferably esters of unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and amides of unsaturated carboxylic acid and aliphatic polyhydric amine compound, and these polymers. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amine group, a mercapto group and the like, monofunctional or polyfunctional isocyanates or epoxy groups, or Dehydration condensation reactant with monofunctional or polyfunctional carboxylic acid, etc. In addition, reactants of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups and epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols have halogen groups or toluene The reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In addition, instead of the unsaturated carboxylic acid, a group of compounds substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether and the like may be used. As these specific compounds, in the present invention, the compounds described in paragraph numbers [0095] to paragraph numbers [0108] of Japanese Patent Laid-Open No. 2009-288705 can also be suitably used.

In addition, the polymerizable compound is preferably a compound containing one or more groups having an ethylenically unsaturated bond and having a boiling point of 100° C. or higher under normal pressure. As an example of this compound, for example, reference can be made to the compounds described in Paragraph No. 0227 of Japanese Patent Laid-Open No. 2013-29760 and Paragraph No. 0254 to No. 0257 of Japanese Patent Laid-Open No. 2008-292970, and the contents can be incorporated To the specification of this application.

The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product is Kayarad (KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is Kayarad (KAYARAD) D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin Nakamura Chemical Co., Ltd.), and these (A The structure in which propylene acetyl group is between the residues of ethylene glycol and propylene glycol (for example, SR454, SR499 commercially available from Sartomer). These oligomer types can also be used. The following shows preferred forms of the polymerizable compound.

The polymerizable compound may have acid groups such as carboxyl groups, sulfonic acid groups, and phosphoric acid groups. The polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid It is particularly preferred that the ester is based on the ester, and the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Examples of commercially available products include M-510 and M-520 which are polyacid-modified acrylic oligomers produced by East Asia Synthesis.

The preferred acid value of the polymerizable compound having an acid group is 0.1 mgKOH/g to 40 mgKOH/g, and particularly preferably 5 mgKOH/g to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH/g or less, it is advantageous in terms of manufacturing or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

As the polymerizable compound, a compound having a structure derived from a cyclic ester (for example, caprolactone, valerolactone, etc., and particularly preferably caprolactone) is also a preferred form. The compound having a structure derived from a lactone is not particularly limited as long as it has a structure derived from a lactone in the molecule, and examples thereof include trimethylolethane or di-trimethylolethane, Polyols such as trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, and trimethylolmelamine are esterified with (meth)acrylic acid and ε-caprolactone The obtained ε-caprolactone is modified polyfunctional (meth)acrylate. Among them, a compound having a structure derived from lactone represented by the following general formula (Z-1) is preferred.

[化41]

In the general formula (Z-1), 6 Rs are all groups represented by the following general formula (Z-2), or 1 to 5 of the 6 Rs are represented by the following general formula (Z-2) ), the remainder is the group represented by the following general formula (Z-3).

[化42]

In the general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

[化43]

In the general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bonding bond.

The polymerizable compound having a structure derived from its own lactone is, for example, commercially available from Nippon Kayaku (KAYARAD) DPCA series, including: DPCA-20 (the above formula (Z-1) to formula In (Z-3), m=1, the number of groups represented by the formula (Z-2)=2, and the compound where R ¹ is a hydrogen atom), DPCA-30 (the formula (Z-1) to the above) In formula (Z-3), m=1, the number of groups represented by (Z-2)=3, and R ¹ are all hydrogen atoms), DPCA-60 (the above formula (Z-1) to In the formula (Z-3), m=1, the number of groups represented by the formula (Z-2)=6, and the compounds where R ¹ are all hydrogen atoms), DPCA-120 (the formula (Z-1) ~ In the formula (Z-3), m=2, the number of groups represented by the formula (Z-2)=6, the compound in which R ¹ is all a hydrogen atom), etc.

As the polymerizable compound, a compound represented by the following general formula (Z-4) or general formula (Z-5) can also be used.

[化44]

In the general formula (Z-4) and the general formula (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O) -, y each independently represent an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group. In the general formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group. In the general formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n independently represents an integer of 0 to 10, and the total of each n represents an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. In addition, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12. In addition, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the general formula (Z-4) or the general formula (Z-5) is preferably The form where the terminal on the oxygen atom side is bonded to X.

The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), it is preferred that the six Xs are all propylene acetyl groups.

The total content of the compound represented by the general formula (Z-4) or the general formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by the following steps: by performing a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide The step of ring-opening skeleton bonding, and the step of reacting the terminal hydroxyl group of the ring-opening skeleton with (meth)acryloyl chloride to introduce a (meth)acryloyl group. Each step is a well-known step, and those skilled in the art can easily synthesize the compound represented by the general formula (Z-4) or the general formula (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferable. Specifically, the compounds represented by the following formula (a) to formula (f) (hereinafter, also referred to as "exemplified compounds (a) to exemplified compounds (f)") are mentioned, and among them, preferred are exemplified compounds (A), exemplified compound (b), exemplified compound (e), exemplified compound (f).

[化45]

[化46]

As a commercially available product of the polymerizable compound represented by the general formula (Z-4) or the general formula (Z-5), for example, a tetrafunctional product having four ethoxylated chains manufactured by Sadoran Corporation can be cited. Acrylic ester SR-494, DPCA-60 as a hexafunctional acrylate with 6 pentanyloxy chains manufactured by Nippon Kayaku Co., Ltd., as a trifunctional acrylate with 3 isobutyleneoxy chains TPA-330 and so on.

In the present invention, as the polymerizable compound, a compound having an epoxy group can also be used. As the compound having an epoxy group, those having two or more epoxy groups in one molecule are preferred. By using a compound having two or more epoxy groups in one molecule, the effect of the invention can be more effectively achieved. Within 1 molecule, the epoxy group is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3.

In the present invention, as the compound having an epoxy group, a structure having two benzene rings connected by a hydrocarbon group can be preferably used. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. In addition, the epoxy group is preferably linked via a linking group. Examples of the linking group include an alkyl group containing an alkyl group, an aryl group, -O-, a hydrogen atom represented by -NR'-(R', a substituent that may have a substituent, or an aryl group that may have a substituent. It is preferably a group represented by a hydrogen atom), at least one of -SO ₂ -, -CO-, -O-, and -S-.

The epoxy equivalent of the compound having an epoxy group (= molecular weight of the compound having an epoxy group/number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 g/eq to 400 g/eq, and More preferably, it is 100 g/eq to 300 g/eq. The effect can be obtained by setting the upper limit of the epoxy equivalent of the compound having an epoxy group to 500 g/eq or less. In terms of practical stability, the lower limit of the epoxy equivalent of the compound having an epoxy group is preferably 100 g/eq or more.

The compound having an epoxy group may be a low-molecular compound (for example, a molecular weight of less than 2000, and further, a molecular weight of less than 1,000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight Any one with an average molecular weight of 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000.

As the compound having an epoxy group having a structure in which two benzene rings are connected by a hydrocarbon group, a compound represented by the following general formula (2a) can be preferably used.

[化47]

In the general formula (2a), R ¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. For details of R ¹ to R ¹⁹ of the general formula (2a), reference can be made to paragraph No. 0036 of Japanese Patent Laid-Open No. 2013-011869, and the contents thereof can be included in the specification of the present application. In particular, R ¹ to R ^{19 are} preferably independently any one of a hydrogen atom, a methyl group, an ethyl group, or a methoxy group. In addition, it is more preferable that at least one selected from R ¹³ , R ¹⁸ and R ¹⁹ is a methyl group. Even more preferably, R ¹³ , R ¹⁸ and R ¹⁹ are methyl groups, and R ¹ to R ¹² and R ¹⁴ to R ¹⁷ are hydrogen atoms. The compound represented by the general formula (2a) can be synthesized with reference to paragraph No. 0036 of Japanese Patent Laid-Open No. 2013-011869. Examples of commercially available products include VG-3101L manufactured by Printec Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd., and the like.

As the compound having an epoxy group, for example, a compound represented by the following general formula (EP1) can be used.

[Chemical 48]

In the formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom, and an alkyl group. The alkyl group may have a cyclic structure, and may further have a substituent. In addition, R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Q ^EP represents a single bond or n ^EP valent organic group. R ^EP1 ～R ^EP3 can be bonded to Q ^EP to form a ring structure. n ^EP represents an integer of 2 or more, preferably 2-10, and more preferably 2-6. However, when Q ^EP is a single bond, n ^EP is 2. For details of R ^EP1 to R ^EP3 and Q ^EP , please refer to the descriptions in paragraph Nos. 0087 to 0088 of Japanese Patent Laid-Open No. 2014-089408, and the contents thereof can be incorporated into the specification of the present application.

Specific examples of the compound having an epoxy group are illustrated below, but the present invention is not limited to these specific examples.

[化50]

[Chem 49]

[化50]

As the compound having an epoxy group, an oligomer or polymer having an epoxy group in the side chain can also be preferably used. Examples of such compounds include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and aliphatic epoxy resin. These compounds may be commercially available products or may be obtained by introducing an epoxy group into the side chain of the polymer. As commercial products, for example, bisphenol A type epoxy resins are JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins (shares)) , EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC (stock)), etc., Bisphenol F Type epoxy resins are JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon (830), Epiclon (EPICLON) 835 (above, Di Aisheng ( Co., Ltd.), LCE-21, RE-602S (above, manufactured by Nippon Kayaku (Co., Ltd.)), etc., phenol novolac epoxy resins are JER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy (share)) Manufacturing), Epiclon (EPICLON) N-740, Epiclon (EPICLON) N-770, Epiclon (EPICLON) N-775 (above, manufactured by Di Aisheng (stock)), etc., cresol novolac type ring Oxygen resins are EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-670, EPICLON N-673, EPICLON N -680, Epiclon (EPICLON) N-690, Epiclon (EPICLON) N-695 (above, manufactured by Di Aisheng (stock)), EOCN-1020 (above, manufactured by Nippon Kayaku (share)), etc., fat Group epoxy resins are ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above, ADEKA) (ADEKA) Shares) Manufacturing), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above, manufactured by Daicel Chemical Industry Co., Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX -321L, EX-850L (above, manufactured by Nagase ChemteX (shares)), etc. In addition to this, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN ) EP-4011S (above, manufactured by Adiko (share)), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by Adico (share)) , JER1031S (manufactured by Japan Epoxy Co., Ltd.), etc. In addition, JER1031S (manufactured by Mitsubishi Chemical Co., Ltd.), JER1032H60 (manufactured by Mitsubishi Chemical Co., Ltd.), Epiclon HP-4700 (manufactured by Di Aisheng Co., Ltd.), and Epiclon (EPICLON) N-695 (manufactured by Di Aisheng (stock) company), Epiclon (EPICLON) 840 (manufactured by Di Aisheng (stock company)), Epiclon (EPICLON) N660 (manufactured by Di Aisheng (stock company)), Epiclon (EPICLON) HP7200 (made by Di Aisheng (stock) company), etc.

In the present invention, as polymerizable compounds, for example, Japanese Patent Laid-Open No. 48-41708, Japanese Patent Laid-Open No. 51-37193, Japanese Patent No. 2-32293, Japanese Patent No. 2-16765 Acrylic urethanes described in the gazette, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 Urethane compounds having an ethylene oxide skeleton described in the Japanese Patent Publication are also suitable. In addition, by using Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238, the molecule has an amine group structure or a sulfide structure The addition of polymerizable compounds, can obtain a coloring composition with very excellent photosensitivity. In addition, in the present invention, a compound having an oxetane group can also be used as a polymerizable compound. Examples of the compound having an oxetanyl group include the compounds described in paragraphs 0134 to 0145 of Japanese Patent Laid-Open No. 2008-224970, and the contents thereof can be incorporated into this specification. As a specific example, ARON OXETANE OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by East Asia Synthetic Co., Ltd.) can be used. Examples of commercially available products of polymerizable compounds include urethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.) , DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha), etc.

In the coloring composition of the present invention, the content of the polymerizable compound relative to the total solid content of the coloring composition is preferably 0.1% by mass to 30% by mass. For example, the lower limit is 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 15% by mass or less. The polymerizable compound may be a single kind, or two or more kinds may be used in combination. When two or more types are used in combination, the total amount preferably falls within the above range.

（式（T1）中，n表示2～4的整數，L表示二價～四價的連結基）<<Multifunctional thiol compound>> The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more thiol groups in the molecule for the purpose of promoting the reaction of the polymerizable compound and the like. The polyfunctional thiol compound is preferably a secondary alkane thiol, and particularly preferably a compound having a structure represented by the following general formula (T1). General formula (T1) [Chem. 51]

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

In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and particularly preferably 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 formula (T2) to structural formula (T4), and the compound represented by the formula (T2) is particularly preferred. These polyfunctional thiols can be used alone or in combination.

[化52]

When the coloring composition of the present invention contains a polyfunctional thiol compound, the content of the polyfunctional thiol relative to the total solid content of the coloring composition is preferably 0.3% by mass to 8.9% by mass, and more preferably 0.8% by mass to 6.4% by mass quality%. In addition, polyfunctional thiols can also be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<<Other Dyestuffs>> The coloring composition of the present invention may contain a dye (hereinafter, also referred to as other dye) other than the dye multimer (A). Either pigment or dye can be preferably used for other pigments, and it is more preferably a pigment for the reason of high resistance to heat or light. Among other pigments, the content of the pigment is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 99% by mass or more relative to the total amount of other pigments. According to this aspect, it is easy to obtain an effect that resistance to heat or light becomes high. As the pigment, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferred.

<<<Dye>>> The dye is not particularly limited, and known dyes used in color filters can be used. For example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent No. No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 505950, U.S. Patent No. 5667920, U.S. Patent Publication No. 5-333207, Japanese Patent Publication No. 6-35183, Japanese Patent Publication Dye disclosed in Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. 6-194828, etc. As the chemical structure, pyrazole azo, pyrrole methylene, anilinoazo, triarylmethane, anthraquinone, benzylidene, oxacyanine, pyrazolotriazole azo can be used Series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole methylimide series dyes.

<<<Pigment>>> Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like or carbon black (C.I. Pigment Black 7). Specific examples of the metal compound include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of metals.

Examples of organic pigments include the following pigments: CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108 , CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167 , CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 199; CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 71; CI Pigment Red 81, CI Pigment Red 105, CI Pigment Red 122 , CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 167, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 209 , CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270; CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32 , CI Pigment Violet 39; CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:3, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22. CI Pigment Blue 60, CI Pigment Blue 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58; CI Pigment Brown 25, CI Pigment Brown 28; CI Pigment Black 1.

The organic pigments can be used alone, or various organic pigments can be used in combination for the purpose of spectral adjustment or color purity improvement. The following shows specific examples of preferred combinations. For example, as the red pigment, anthraquinone-based pigments, perylene-based pigments, diketopyrrolopyrrole-based pigments may be used alone, or at least one of these pigments may be used in combination with the disazo-based yellow pigments and isoindoline-based yellow pigments. , A mixture of quinophthalone yellow pigment or perylene red pigment. For example, examples of anthraquinone pigments include CI Pigment Red 177, examples of perylene pigments include CI Pigment Red 155 and CI Pigment Red 224, and examples of diketopyrrolopyrrole pigments include CI Pigment Red 254. From the viewpoint of color properties, it is preferably mixed with CI Pigment Yellow 139. In addition, the quality of the red pigment and the yellow pigment is preferably in the range of 100:5 to 100:50, and more preferably in the range of 100:10 to 100:30. In the case of a combination of red pigments, it can be adjusted in accordance with the required spectral distribution. As the green pigment, a halogenated phthalocyanine-based pigment may be used alone, or a mixture thereof with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, a methylenimine-based yellow pigment, or an isoindolin-based yellow pigment may be used. For example, as such an example, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or Mix of CI Pigment Yellow 185. The quality of the green pigment and the yellow pigment is preferably in the range of 100:5 to 100:150, and more preferably in the range of 100:30 to 100:120. As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture thereof with a dioxazine-based purple pigment may be used. For example, a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is preferably 100:0 to 100:100. As the pigment for the black matrix, carbon, titanium black, iron oxide, or titanium oxide may be used alone, or a mixture of two or more of these pigments may be used, and a combination of carbon and titanium black is preferable. In addition, the quality of carbon and titanium black is preferably in the range of 100:0 to 100:60.

The primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness or contrast when used as a color filter, and from the viewpoint of dispersion stability Above 5 nm. The primary particle diameter of the pigment is more preferably 5 nm to 75 nm, further preferably 5 nm to 55 nm, and particularly preferably 5 nm to 35 nm. The primary particle diameter of the pigment can be measured by a well-known method such as an electron microscope. Among them, the pigment is preferably a pigment selected from the group consisting of anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, methylimine pigments, and dioxazine pigments. In particular, CI Pigment Red 177 (anthraquinone pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58 and CI Pigment Blue 15:6 are preferred. Phthalocyanine pigments), CI Pigment Yellow 138 (quinophthalone pigments), CI Pigment Yellow 139, CI Pigment Yellow 185 (isoindoline pigments), CI Pigment Yellow 150 (methyl imine pigments), CI Pigment Violet 23 (two Oxazine pigment).

When the coloring composition of the present invention contains other pigments, the content of the other pigments is preferably 10% by mass to 70% by mass, more preferably 25% by mass to 65% by mass relative to the total solid content of the coloring composition, and even more It is preferably 35% by mass to 55% by mass. The coloring composition of the present invention may contain only one other pigment, or two or more types. When two or more kinds are contained, the total amount is preferably within the above range.

<<Resin>> The coloring composition of the present invention preferably contains a resin. Examples of the resin include resins that disperse pigments (dispersion resins), alkali-soluble resins, and the like.

<<<Dispersion resin>>> Examples of the dispersion resin include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, Modified polymer dispersants such as poly(meth)acrylates, (meth)acrylic copolymers, and formalin naphthalenesulfonate condensates. Polymer dispersants can be further classified into linear polymers, terminal modified polymers with fixed sites on the surface of the pigment, grafted polymers with fixed sites on the surface of the pigment, and pigments based on their structure. Block type polymer on the fixed part of the surface.

Examples of the terminal-modified polymer having a fixed portion for the surface of the pigment include, for example, those having a phosphate group at the terminal as described in Japanese Patent Laid-Open No. 3-112992 and Japanese Patent No. 2003-533455. Polymers, polymers having sulfonic acid groups at the ends described in Japanese Patent Laid-Open No. 2002-273191, etc., partial skeletons or heterocycles having organic dyes described in Japanese Patent Laid-Open No. 9-77994, etc. Of polymers. In addition, as described in Japanese Patent Laid-Open No. 2007-277514, two or more fixing sites (acid groups, basic groups, partial skeletons of organic dyes, or heterocyclic rings, etc.) on the surface of the pigment are introduced into the polymer terminal. The dispersion stability of the molecules is also excellent and better.

Examples of the graft-type polymer having a fixed portion on the surface of the pigment include polyester resins. Specifically, the poly(lower alkylene group described in Japanese Patent Laid-Open No. 54-37082, Japanese Patent Laid-Open No. 8-507960, Japanese Patent Laid-Open No. 2009-258668, etc. can be cited. Amine) and polyester reaction product, the reaction product of polyallylamine and polyester described in Japanese Patent Laid-Open No. 9-169821, etc., Japanese Patent Laid-Open No. 10-339949, Japanese Patent Laid-Open 2004 -Copolymer of macromonomer and nitrogen atom monomer described in JP-37986, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732 A graft polymer having a partial skeleton or a heterocyclic ring of an organic dye described in the gazette, etc., a copolymer of a macromonomer and an acid group-containing monomer described in Japanese Patent Laid-Open No. 2010-106268, etc. Wait. In particular, from the viewpoint of the dispersibility, dispersion stability of the pigment dispersion, and the developability exhibited by the coloring composition using the pigment dispersion, it is particularly preferable to have the properties described in Japanese Patent Laid-Open No. 2009-203462 Amphoteric resin of basic group and acid group.

As the macromonomer used when producing the graft-type polymer by radical polymerization, a well-known macromonomer can be used, and examples thereof include macromonomer AA-6 (terminal Polymethyl methacrylate with a methacryl group), AS-6 (polystyrene with a methacryl group as the terminal group), AN-6S (styrene with methacryl group as the terminal group) Copolymer of acrylonitrile), AB-6 (polybutyl acrylate with methacryloyl group as the terminal group), Placcel FM5 (2-hydroxymethacrylate) manufactured by Daicel Chemical Industry Co., Ltd. Ε-caprolactone 5-mole equivalent adduct of ethyl ester), FA10L (ε-caprolactone 10-mole equivalent adduct of 2-hydroxyethyl acrylate), and Japanese Patent Laid-Open No. 2-272009 The polyester-based macromonomer described in the above. Among these, from the viewpoint of the dispersibility, dispersion stability of the pigment dispersion, and the developability exhibited by the coloring composition using the pigment dispersion, it is preferably a polyester which is flexible and excellent in lyophilic properties The macromonomer is particularly preferably a polyester macromonomer represented by the polyester macromonomer described in Japanese Patent Laid-Open No. 2-272009.

As the block-type polymer having a fixed portion on the surface of the pigment, the block-type polymer described in Japanese Patent Laid-Open No. 2003-49110, Japanese Patent Laid-Open No. 2009-52010, etc. is preferable.

The resin can also be obtained as a commercially available product. Examples of such specific examples include "DA-7301" manufactured by Nanmu Chemical Co., Ltd. and "Disperbyk" manufactured by BYK Chemie. )-101 (polyamide amine phosphate), Disperbyk-107 (carboxylate), Disperbyk-110 (copolymer containing acid groups), Disper Disperbyk-130 (polyamide), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk (Disperbyk)-164, Disperbyk-165, Disperbyk-166, Disperbyk-170 (polymer copolymer)", "BYK- P104, BYK-P105 (High Molecular Weight Unsaturated Polycarboxylic Acid), "EFKA (EFKA) 4047, EFKA (EFKA) 4050 ~ EFKA (EFKA) 4010 ~ manufactured by EFKA (EFKA) Efka (EFKA) 4165 (polyurethane system), Efka (EFKA) 4330 ~ Efka (EFKA) 4340 (block copolymer), Efka (EFKA) 4400-Efka (EFKA) 4402 (modified polyacrylate), Efka (EFKA) 5010 (polyester amide), Efka (EFKA) 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 ( Fatty acid polyester), Efka (EFKA) 6745 (phthalocyanine derivative), Efka (EFKA) 6750 (azo pigment derivative)", "Ajinomoto Fine-Techno" Ajisper (PB821), Ajisper (PB822), Ajisper (PB880), Ajisper (PB881), "Florene (Florene) manufactured by Kyoeisha Chemical Company ) TG-710 (urethane oligomer), Polyflow No. 50E, Polyflow No. 300 (acrylic copolymer)", manufactured by Nanben Chemical Co., Ltd. Disparlon KS-860, Disparlon 873SN, Disparlon 874, Disparlon #2150 (aliphatic polycarboxylic acid), Disparon (Disparlon) #7004 (polyetherester), Disparlon DA-703-50, Displon arlon) DA-705, Disparlon DA-725, "Demol RN, Demol N (formalin polycondensate of naphthalene sulfonate), Demo Demol MS, Demol C, Demol SN-B (Formalin polycondensate of aromatic sulfonic acid)", "Homogenol L-18 (high molecular weight Carboxylic acid), Emalgen (Emalgen) 920, Emalgen (Emalgen) 930, Emalgen (Emalgen) 935, Emalgen (Emalgen) 985 (polyoxyethylene nonylphenyl ether), astaxanthin (Acetamin) 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivatives), Solsperse manufactured by Lubrizol (shares), Japan 22000 (azo pigment derivative), Sonupas (Solsperse) 13240 (polyesteramine), Sonupas (Solsperse) 3000, Sonupas (Solsperse) 17000, Sonupas (Solsperse) 27000 ( Polymer with functional part at the end), Sonupas (Solsperse) 24000, Sonupas (Solsperse) 28000, Sonupas (Solsperse) 32000, Sonupas (Solsperse) 38500 (graft type high "Molecule"", "Nikol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikko Chemicals, "Hinoact T-8000E" manufactured by Kawaken Fine Chemicals (shares), "Organic Siloxane Polymer KP341" manufactured by Shin-Etsu Chemical Industries (shares), Yushang ( Shares) manufactured by "W001: cationic surfactants, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl Nonionic surfactants such as phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters, and anionic interfaces such as "W004, W005, W017" "Activator", "Efka (EFKA) -46, Efka (EFKA) -47, Efka (EFKA) -47EA, Efka Polymer (EFKA Polymer) 100," EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", SINO "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 15, Disper" manufactured by Sannopco (shares) Disperse Aid 9100" and other polymer dispersants, "Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic" F38, and Adecoplan Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68 , Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic P84, Adeka Pluronic P84 (Adeka Pluronic) F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123", and "Ionet (trade name) S-20" manufactured by Sanyo Chemical Co., Ltd., etc. .

The resin may be used alone or in combination of two or more. In addition, the resin may also include a terminal-modified polymer having a fixed portion on the surface of the pigment, a graft polymer having a fixed portion on the surface of the pigment, and a block-type polymer having a fixed portion on the surface of the pigment. The alkali-soluble resin is used together. Examples of the alkali-soluble resin include (meth)acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc., and side chains The acidic cellulose derivative having a carboxylic acid and a resin obtained by modifying an acid anhydride in a polymer having a hydroxyl group are particularly preferably (meth)acrylic copolymers. In addition, the N-substituted maleimide diimide monomer copolymer described in Japanese Patent Laid-Open No. 10-300922, the ether dimer copolymer described in Japanese Patent Laid-Open No. 2004-300204, The alkali-soluble resin containing a polymerizable group described in Japanese Patent Laid-Open No. 7-319161 is also preferable.

When the dispersing resin is contained in the coloring composition, the content of the dispersing resin is preferably 1 part by mass to 100 parts by mass relative to 100 parts by mass of the pigment. For example, the lower limit is more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more. For example, the upper limit is more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less.

<<<Alkali-soluble resin>>> The coloring composition of the present invention may contain an alkali-soluble resin as a resin. By containing an alkali-soluble resin, developability and pattern formability are improved. Furthermore, an alkali-soluble resin can also be used as the dispersion resin. The molecular weight of the alkali-soluble resin is not particularly limited, and the weight average molecular weight (Mw) is preferably 5,000 to 100,000. In addition, the number average molecular weight (Mn) is preferably 1,000 to 20,000. The alkali-soluble resin may also be a linear organic polymer polymer, and may have at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Appropriate choice among alkali soluble resins.

The alkali-soluble resin will be described. As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxystyrene-based resins, polysiloxane-based resins, acrylic resins, acrylamide-based resins, and acrylic/acrylamide copolymer resins are preferred. From the viewpoint of controlling developability, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred. Examples of groups that promote alkali solubility (hereinafter also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Preferably, they are soluble in organic solvents and can be carried out by a weakly alkaline aqueous solution The base for development is particularly preferably a (meth)acrylic acid. These acid groups may be only one kind, or two or more kinds.

When manufacturing an alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when producing an alkali-soluble resin by a radical polymerization method can be easily set by those skilled in the art, and the conditions can also be experimentally specified.

The alkali-soluble resin is preferably a polymer having a carboxylic acid in the side chain, and examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, and maleic acid copolymers. Partially esterified maleic acid copolymers, novolac-type resins and other alkali-soluble phenol resins, and acidic cellulose derivatives having a carboxyl group on the side chain, and an acid anhydride is added to a polymer having a hydroxyl group. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and vinyl compounds. Examples of the alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Esters, tolyl (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. Examples of vinyl compounds include styrene, α-methylstyrene, vinyltoluene, and methyl Glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., as The N-substituted maleimide diimide monomer described in Japanese Patent Laid-Open No. 10-300922 includes N-phenyl maleimide diimide and N-cyclohexyl maleimide diimide. Amines. Furthermore, the other monomers copolymerizable with (meth)acrylic acid may be only one kind, or two or more kinds.

In addition, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may also be used. Examples of the polymerizable group include (meth)allyl and (meth)acryloyl. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing a polymerizable group on the side chain is useful. The alkali-soluble resin containing a polymerizable group is preferably a resin or the like: a urethane-modified alkali-soluble resin obtained by reacting the following compound with an acrylic resin containing a carboxyl group, the compound having an isocyanate in advance A group reacts with a hydroxyl group, leaving an unreacted isocyanate group, and contains a polymerizable group such as a (meth)acryloyl group; an acrylic resin containing a carboxyl group and a compound having an epoxy group and a polymerizable double bond in the molecule Alkali-soluble resin obtained by the reaction; acid-side epoxy acrylate resin; alkali-soluble resin obtained by reacting a hydroxyl-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond; and a hydroxyl-containing acrylic resin Alkali-soluble resin obtained by reacting with isocyanate and a compound having a polymerizable group; by having a side chain described in Japanese Patent Laid-Open No. 2002-229207 and Japanese Patent Laid-Open No. 2003-335814 The alkali-soluble resin obtained by performing an alkaline treatment on an ester-based resin is based on a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position. Examples of the alkali-soluble resin containing a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (COOH-containing acrylic polyurethane oligomer (Polyurethane acrylic oligomer), made by Diamond Shamrock Co. Ltd., Viscoat R-264, KS Resist106 (all made by Osaka Organic Chemical Industry Co., Ltd.), SEC Rome (Cyclomer) P series, Placcel CF200 series (all made by Daicel-Chemical Co., Ltd.), Ebecryl 3800 (made by Daicel-UCB) ), Acrycure (Acrycure)-RD-F (manufactured by Japan Catalyst Company), etc.

As the alkali-soluble resin, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer can be preferably used , Multi-component copolymers containing benzyl (meth)acrylate/(meth)acrylic acid/other monomers. In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth)acrylate/polystyrene described in Japanese Patent Laid-Open No. 7-140654 Macromonomer/benzyl methacrylate/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/A Benzyl acrylate/methacrylic acid copolymer, etc.

It is also preferable that the alkali-soluble resin contains a polymer (a) obtained by polymerizing the following monomer components containing the compound represented by the following general formula (ED) and/or the following general formula The compound represented by (ED2) (hereinafter, these compounds are sometimes referred to as "ether dimers").

通式（ED）[化53]

General formula (ED)

通式（ED2）中，R表示氫原子或碳數1～30的有機基。作為通式（ED2）的具體例，可參考日本專利特開2010-168539號公報的記載。In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a C 1-25 hydrocarbon group which may have a substituent. General formula (ED2) [Chem 54]

In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), reference can be made to the description in Japanese Patent Laid-Open No. 2010-168539.

In the general formula (ED), the C 1-25 hydrocarbon group which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, and iso Linear or branched alkyl groups such as propyl, n-butyl, isobutyl, third butyl, third pentyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; 1-methyl Alkoxy-substituted alkyl groups such as oxyethyl and 1-ethoxyethyl; aryl-substituted alkyl groups such as benzyl. Among these, from the viewpoint of heat resistance, particularly preferred are substituents of primary carbon or secondary carbon that are not easily detached by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl, and the like.

Specific examples of the ether dimer include, for example, dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxygen Bis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(isopropyl) -2,2'-[oxobis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxobis(methylene)]bis-2-acrylic acid Ester, di(isobutyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(third butyl)-2,2'-[oxobis(methylene (Methyl)]bis-2-acrylate, di(third pentyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(stearyl)-2, 2'-[oxobis(methylene)]bis-2-acrylate, di(lauryl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di( 2-ethylhexyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxobis( Methylene)]bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl-2 ,2'-[oxobis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxobis(methylene)]bis-2-acrylate, dicyclohexyl -2,2'-[oxobis(methylene)]bis-2-acrylate, di(third butylcyclohexyl)-2,2'-[oxobis(methylene)]bis- 2-acrylate, di(dicyclopentadienyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(tricyclodecyl)-2,2' -[Oxobis(methylene)]bis-2-acrylate, di(isobornyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, diadamantane Yl-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxobis(methylene Radical)] bis-2-acrylate etc. Among these, particularly preferred are dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxobis(methylene Group)] bis-2-acrylate, dicyclohexyl-2,2'-[oxobis(methylene)] bis-2-acrylate, dibenzyl-2,2'-[oxobis( Methylene)] bis-2-acrylate. These ether dimers may be only one kind, or two or more kinds. The structure derived from the compound represented by the general formula (ED) may also be copolymerized with other monomers.

式（X）中，R₁ 表示氫原子或甲基，R₂ 表示碳數2～10的伸烷基，R₃ 表示氫原子或可含有苯環的碳數1～20的烷基。n表示1～15的整數。The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X). [化55]

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

In the formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. In addition, the alkyl group of R ₃ has a carbon number of 1 to 20, preferably 1 to 10, and the alkyl group of R ₃ may contain a benzene ring. Examples of the benzene ring-containing alkyl group represented by R ₃ include benzyl group and 2-phenyl(iso)propyl group.

For the alkali-soluble resin, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to [0685] to [0700] of US Patent Application Publication No. 2012/0235099), and those contents Can be incorporated into the specification of this application. Furthermore, the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 described in Japanese Patent Laid-Open No. 2012-32767 and the alkali-soluble resin used in the examples, and Japanese Patent Laid-Open No. 2012- can also be used The binder resin described in paragraph No. 0088 to paragraph No. 0098 of 208474 and the binder resin used in the examples, the binder described in paragraph No. 0022 to paragraph No. 032 of Japanese Patent Laid-Open No. 2012-137531 Resin and binder resin used in the examples, binder resin described in Paragraph No. 0132 to Paragraph No. 0143 of Japanese Patent Laid-Open No. 2013-024934 and binder resin used in the examples, Japanese Patent Laid-Open Paragraph No. 0092 to Paragraph No. 0098 of 2011-242752 and the binder resin used in the Examples, and the binder resin described in Paragraph No. 0030 to Paragraph No. 072 of Japanese Patent Laid-Open No. 2012-032770. These contents can be incorporated into the specification of this application.

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

When the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin relative to the total solid content of the coloring composition is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 12% by mass, and even more preferably It is 3% by mass to 10% by mass. The coloring composition of the present invention may contain only one alkali-soluble resin, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<<Pigment derivative>> The coloring composition of the present invention may contain a pigment derivative. The pigment derivative refers to a compound having a structure in which a part of a pigment is substituted with an acidic group, a basic group, phthalimidomethyl group, or the like. As the pigment derivative, from the viewpoint of dispersibility and dispersion stability, a pigment derivative having an acidic group or a basic group is preferred. Examples of the pigments that constitute the pigment derivatives include pyrrolopyrrole pigments, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, and violet rings Ketone pigments, perylene pigments, sulfur indigo pigments, isoindolino pigments, isoindolino pigments, quinophthalone pigments, threne pigments, metal complex pigments, etc. As the acid group possessed by the pigment derivative, a sulfonic acid group, a carboxylic acid group and its quaternary ammonium salt are preferred, a carboxylic acid group and a sulfonic acid group are more preferred, and a sulfonic acid group is particularly preferred. The basic group of the pigment derivative is preferably an amine group, and particularly preferably a tertiary amine group. The content of the pigment derivative is preferably 1% by mass to 50% by mass relative to the total mass of the pigment, and more preferably 3% by mass to 30% by mass. The pigment derivative may contain only one kind or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<<Photopolymerization initiator>> The coloring composition of the present invention may further contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to start the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity from the ultraviolet region to visible rays are preferred. In addition, it may be an active agent that produces a certain action with a photo-excited sensitizer to generate active radicals, or may be an initiator that starts cationic polymerization according to the type of monomer. In addition, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), amide phosphine compounds such as amide phosphine oxide, hexaarylbiimidazole, and oxime derivatives Oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc.

In addition, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acetylphosphine compounds, Phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene- Compounds in the group consisting of iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acetylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, styrene Ketone compounds, particularly preferably at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds .

In particular, when the coloring composition of the present invention is used for manufacturing a color filter of a solid-state imaging element, since it is necessary to form a fine pattern in a sharp shape, it is important to harden and leave no residue on the unexposed portion development. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging element, stepwise exposure is used for exposure for curing. This exposure machine is sometimes damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator. Considering these aspects, when forming a fine pattern like a solid-state imaging element, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In addition, by using an oxime compound, the color shift property can be further improved. As a specific example of the photopolymerization initiator, for example, reference can be made to paragraph 0265 to paragraph 0268 of Japanese Patent Laid-Open No. 2013-29760, and the content thereof can be incorporated into the specification of the present application.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969, and an acetylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. As hydroxyacetophenone-based initiators, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRANC can be used Solid (IRGACURE) -127 (trade name: all made by BASF). As the aminoacetophenone-based initiator, commercially available products of IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all Made for BASF). As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wavelength light source such as 365 nm or 405 nm can also be used. As an acylphosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF), which are commercially available products, can be used.

As the photopolymerization initiator, oxime compounds are more preferred. As specific examples of the oxime initiator, the compounds described in Japanese Patent Laid-Open No. 2001-233842, the compounds described in Japanese Patent Laid-Open No. 2000-80068, and the compounds described in Japanese Patent Laid-Open No. 2006-342166 can be used compound of. In the present invention, examples of the oxime compound that can be suitably used include, for example, 3-benzyloxyiminobutane-2-one and 3-ethoxyiminobutane-2-one. , 3-propionoxyiminobutane-2-one, 2-ethoxyiminopentan-3-one, 2-ethoxyimino-1-phenylpropane-1 -Ketone, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxy Carbonyloxyimino-1-phenylpropane-1-one and the like. In addition, you can also list: "Journal of the British Chemical Society, Berkins II (JCS Perkin II)" (1979) pp.1653-1660, "Journal of the British Chemical Society, Berkins II" (1979 ) Pp.156-162, "Journal of Photopolymer Science and Technology (Journal of Photopolymer Science and Technology)" (1995) pp.202-232, Japanese Patent Laid-Open Publication No. 2000-66385, Japanese Patent The compounds described in each of Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, and Japanese Patent Laid-Open No. 2006-342166. For commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be suitably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkls (Adeka Arkls) NCI-831 and Adeka Arkls (Adeka Arkls) NCI-930 (Aidike Manufactured by the company).

In addition, as an oxime compound other than the above description, a compound described in Japanese Patent Laid-Open No. 2009-519904 with an oxime linked to the N position of carbazole, and a hetero substituent introduced into the benzophenone site The compound described in US Patent No. 7626957, the compound described in Japanese Patent Laid-Open No. 2010-15025 and the US Patent Publication No. 2009-292039, and the International Publication Patent No. 2009-131189 The ketoxime compound described in the gazette, the compound described in U.S. Patent No. 7556910 containing the triazine skeleton and the oxime skeleton in the same molecule, and the Japanese patent having a maximum absorption at 405 nm and good sensitivity to a g-ray light source The compounds described in Japanese Patent Application Laid-Open No. 2009-221114. For example, it is preferable to refer to paragraph 0274 to paragraph 0275 of Japanese Patent Laid-Open No. 2013-29760, the content of which can be incorporated into the specification of the present application. Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). Furthermore, the N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[化56]

In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group. Examples of the monovalent non-metallic atomic group include alkyl groups, aryl groups, acetyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. In addition, these groups may have more than one substituent. In addition, the substituent may be further substituted with other substituents. Examples of the substituent include halogen atom, aryloxy group, alkoxycarbonyl group or aryloxycarbonyl group, acetyloxy group, acetyl group, alkyl group, aryl group and the like. In the general formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have more than one substituent. As the substituent, the substituent may be exemplified. In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynyl group. These groups may have more than one substituent. As the substituent, the substituent may be exemplified.

The following shows specific examples of the compound represented by the general formula (OX-1), but the present invention is not limited to these specific examples.

[化57]

The oxime compound has a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, preferably a maximum absorption wavelength in the wavelength range of 360 nm to 480 nm, and particularly preferably has high absorbance in 365 nm and 405 nm Oxime compounds. 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 particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method, for example, it is preferably a UV-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian), and ethyl acetate is used. The solvent was measured at a concentration of 0.01 g/L. The photopolymerization initiator used in the present invention may be used in combination of two or more types as needed.

When the coloring composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator relative to the total solid content of the coloring composition is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and more preferably 1% to 20% by mass. Within this range, better sensitivity and pattern formability can be obtained. The composition of the present invention may contain only one kind of photopolymerization initiator or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<<Other components>> In addition to the above-mentioned components, the coloring composition of the present invention may also contain a solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid within a range that does not impair the effects of the present invention , Organic carboxylic anhydride and other components.

<<<Organic Solvent>>> The coloring composition of the present invention may contain a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the coloring composition, but it is preferable to consider the solubility, coatability, and safety of the dye polymer (A), polymerizable compound, etc. Sex to choose.

As the solvent, examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. Ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-oxypropionic acid alkyl esters (for example: 3 -Methyloxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, etc.)), alkyl esters of 2-oxypropionate (for example: methyl 2-oxypropionate, ethyl 2-oxypropionate, propylene 2-oxypropionate Esters, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Acid ethyl ester)), 2-oxy-2-methyl propionic acid methyl ester and 2-oxy-2-methyl propionic acid ethyl ester (such as 2-methoxy-2-methyl propionic acid methyl ester, 2-Ethoxy-2-methyl ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Methyl esters, ethyl 2-oxobutyrate, etc. As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve can be suitably mentioned. Acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ether Acetate, propylene glycol propyl ether acetate, etc. As ketones, for example, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, etc., and as aromatic Examples of the group hydrocarbons include toluene and xylene.

From the viewpoints of the solubility of the dye polymer (A), polymerizable compound, etc., and improvement of the coating surface shape, it is also preferable to mix two or more of these solvents. For example, it is preferably a mixed solution containing a mixture of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, Ethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate Two or more of ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the coloring composition becomes 5 to 80% by mass. For example, the lower limit is more preferably 5% by mass or more, and still more preferably 10% by mass or more. For example, the upper limit is more preferably 60% by mass or less, and still more preferably 50% by mass or less. The coloring composition of the present invention may contain only one kind of solvent or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<<<Crosslinking agent>>> The coloring composition of the present invention may contain a crosslinking agent. By containing a cross-linking agent, the hardness of the obtained cured film can be further increased. The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. For example, (a) epoxy resin; (b) melamine compound, guanamine compound, glycoluril substituted with at least one substituent selected from hydroxymethyl, alkoxymethyl, and acetylmethyl Compound or urea compound; (c) Phenol compound, naphthol compound or hydroxyanthracene compound substituted with at least one substituent selected from hydroxymethyl, alkoxymethyl, and acetylmethyl. Among them, polyfunctional epoxy resins are preferred. For details of specific examples and the like of the crosslinking agent, refer to paragraphs 0134 to 0147 of Japanese Patent Laid-Open No. 2004-295116, and the contents thereof can be incorporated into the specification of the present application. When the coloring composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is not particularly limited, but it is preferably 2% by mass to 30% by mass, and more preferably 3% by mass relative to the total solid content of the coloring composition % ~ 20% by mass. The coloring composition of the present invention may contain only one kind of crosslinking agent or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<<<Polymerization inhibitor>>> In the coloring composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during the manufacturing process or storage process of the coloring composition, it is desirable to add a small amount of polymerization Inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4 '-Thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosobenzene Trivalent cerium salt of hydroxylamine. When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably about 0.01% by mass to 5% by mass relative to the mass of the colored composition. The coloring composition of the present invention may contain only one kind of polymerization inhibitor, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<<Surface Active Agent>>> In the coloring composition of the present invention, various surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

For example, by containing a fluorine-based surfactant, the liquid characteristics (especially fluidity) at the time of preparation as a coating liquid are further improved. That is, when a coloring composition containing a fluorine-based surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid is reduced, thereby improving the wettability of the coated surface, and The coatability of the coated surface is improved. Therefore, it is effective from the viewpoint that even when a thin film of about several μm is formed with a small amount of liquid, a film with a uniform thickness and a small thickness can be formed more uniformly.

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

Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac. ) F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, manufactured by Di Aisheng (stock)), Fluorad FC430, Flo Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M (shares)), Surflon S-382, Surflon SC-101, Shafu Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Shafuron ( Surflon) SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (OMNOVA) Manufacturing) etc.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (eg, glycerol propoxylate, Glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Ethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, manufactured by BASF), 25R2, Tetronic (Tetronic) 304, 701, 704, 901, 904, 150R1), Sonupas (Solsperse) 20000 (Lubrizol (share)), etc.

Specific examples of the cationic surfactants include phthalocyanine derivatives (trade name: Efka (EFKA)-745, manufactured by Morishita Industry Co., Ltd.), and organosiloxane polymer KP341 (Shin-Etsu Chemical Industry) (Manufactured by shares), (meth)acrylic (co)polymer Polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yushang (Share manufacturing) etc.

Specific examples of the anionic surfactants include W004, W005, and W017 (produced by Yushang Co., Ltd.).

Examples of silicone surfactants include "Toray Silicone DC3PA" manufactured by Toray Dow Corning Corporation, "Toray Silicone SH7PA", and "Toray Silicone" (Toray Silicone DC11PA), "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH29PA", "Toray Silicone (Toray Silicone) SH29PA" Silicone) SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-" manufactured by Momentive Performance Materials "4460", "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shinetsu silicone Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemical Wait.

When the surfactant is included in the coloring composition of the present invention, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass relative to the total mass of the coloring composition. . The coloring composition of the present invention may contain only one kind of surfactant, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

<<<Organic carboxylic acid, organic carboxylic anhydride>>> The coloring composition of this invention may contain organic carboxylic acid and/or organic carboxylic anhydride. The molecular weight of the organic carboxylic acid and the organic carboxylic acid anhydride is preferably 1,000 or less. As specific examples of the organic carboxylic acid and the organic carboxylic acid anhydride, for example, reference can be made to paragraph 0338 to paragraph 0340 of Japanese Patent Laid-Open No. 2013-29760, and the contents thereof can be incorporated into the specification of the present application. When the coloring composition of the present invention contains an organic carboxylic acid and/or organic carboxylic anhydride, the content of the organic carboxylic acid and/or organic carboxylic anhydride is preferably 0.01% by mass to 10% by mass relative to the total solid content of the colored composition %, more preferably 0.03% by mass to 5% by mass, and still more preferably 0.05% by mass to 3% by mass. The coloring composition of the present invention may contain only one organic carboxylic acid and/or organic carboxylic acid anhydride, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

In the coloring composition of the present invention, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, etc. can be formulated as needed. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Laid-Open No. 2004-295116, and these contents can be incorporated into the specification of the present application. The coloring composition of the present invention may contain the sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Laid-Open No. 2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the same.

<The preparation method of a coloring composition> The coloring composition of this invention is prepared by mixing the said component. When preparing a coloring composition, each component constituting the coloring composition may be prepared at one time, or each component may be dissolved and dispersed in a solvent and then sequentially prepared. In addition, there are no particular restrictions on the order of input or operating conditions during the deployment. For example, all components can be dissolved and dispersed in a solvent at the same time to prepare a composition. If necessary, each component can be suitably prepared into two or more solutions/dispersions, which are used during application (during coating). The solution and dispersion are mixed and prepared as a composition. In order to remove foreign substances or reduce defects, the coloring composition of the present invention is preferably filtered by a filter. The filter can be used without particular limitation as long as it has been used for filtering purposes and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, and polyolefin resins (high density, such as polyethylene and polypropylene (PP)) can be used. , Containing ultra-high molecular weight) and other filters. Among these raw materials, polypropylene (including high-density polypropylene) is preferred. The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm. By setting this range, it is possible to surely remove fine foreign matters that hinder the preparation of a uniform and smooth coloring composition in the subsequent steps.

When using filters, different filters can also be combined. At this time, the filtration by the first type filter may be performed only once, or may be performed twice or more. In addition, the first type of filters having different pore sizes may be combined within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, Pall Co., Ltd., Advantec Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Japan Mico) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd. As the second filter, a filter formed of the same material as that of the first filter can be used. For example, the filtration using the first type filter can be performed only in the dispersion liquid, and after mixing other components, the second filtration can be performed.

Since the coloring composition of the present invention can form a cured film having good light resistance, color shift and flatness, it can be suitably used to form a coloring layer of a color filter. In addition, the coloring composition of the present invention can be suitably used as a solid-state imaging element such as a charge coupled element (CCD), a complementary metal oxide semiconductor (CMOS), or an image display device such as a liquid crystal display device The coloring composition for forming the coloring pattern of the color filter and the like. Furthermore, it can also be suitably used for manufacturing purposes of printing ink, inkjet ink, paint, and the like. Among them, it can be suitably used for the manufacture of color filters for solid-state imaging elements such as CCD and CMOS.

<Color Filter, Pattern Forming Method, and Color Filter Manufacturing Method> Next, the color filter, pattern forming method, and color filter of the present invention will be described in detail through its manufacturing method. In addition, a method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

The color filter of the present invention is obtained by using the coloring composition of the present invention. The pattern forming method of the present invention applies the coloring composition of the present invention to a support to form a coloring composition layer, and removes unnecessary portions to form a coloring pattern. The pattern forming method of the present invention can be suitably applied to the formation of coloring patterns of color filters. The pattern forming method of the present invention can be patterned by a so-called photolithography method, or can be patterned by a dry etching method. That is, the first aspect of the method for manufacturing a color filter of the present invention includes the steps of applying the coloring composition of the present invention to a support to form a coloring composition layer, and exposing the coloring composition layer into a pattern, And the step of developing and removing the unexposed portion to form a colored pattern. If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed coloring pattern (post-baking step) may also be provided. In addition, the second aspect of the method of manufacturing the color filter of the present invention includes the steps of applying the coloring composition of the present invention to a support to form a coloring composition layer and hardening it to form a coloring layer; A step of forming a photoresist layer; a step of obtaining a resist pattern by patterning the photoresist layer through exposure and development; and dry etching the colored layer using the resist pattern as an etching mask And the step of forming the coloring pattern. The color filter of the present invention can be suitably obtained by the aforementioned manufacturing method. These will be described in detail below.

<<Step of forming a coloring composition layer>> In the step of forming a coloring composition layer, the coloring composition of the present invention is applied to a support to form a coloring composition layer.

As the support, for example, a substrate for a solid-state imaging element in which a solid-state imaging element (light-receiving element) such as CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used. The coloring pattern in the present invention may be formed on the solid-state imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the non-solid-state imaging element forming surface side (rear surface). In order to improve the adhesion to the upper layer, prevent the diffusion of substances, or to flatten the surface of the substrate, an undercoat layer may be provided on the support as necessary.

As a method of applying the coloring composition of the present invention to a support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing method can be used.

The drying (pre-baking) of the coloring composition layer applied on the support can be carried out at a temperature of 50°C to 140°C for 10 seconds to 300 seconds by a hot plate, an oven, or the like.

«<Pattern formation by photolithography (first form)»>«<<Exposurestep>>> Next, the coloring composition layer formed on the support is exposed to a pattern (exposure step) . For example, using an exposure device such as a stepper, the coloring composition layer formed on the support body is exposed through a mask having a predetermined mask pattern, whereby pattern exposure can be performed. By this, the exposed portion can be hardened. As radiation (light) usable at the time of exposure, ultraviolet rays such as g-rays and i-rays (i-rays are particularly preferred) can be preferably used. The irradiation amount (exposure amount) is preferably, for example, 30 mJ/cm ² to 1500 mJ/cm ² , more preferably 50 mJ/cm ² to 1000 mJ/cm ² , and most preferably 80 mJ/cm ² to 500 mJ/cm ² .

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2 μm to 0.8 μm. By setting the film thickness to 1.0 μm or less, it is easy to obtain high resolution and high adhesion.

<<<Pattern Forming Step>>> Next, the unexposed part is developed and removed to form a coloring pattern (pattern forming step). The development and removal of the unexposed portion can be performed using a developer. Thereby, the coloring composition layer of the unexposed portion in the exposure step is eluted into the developer, and only the photohardened portion remains. As the developer, an organic alkaline developer that does not cause damage to the underlying solid-state imaging element, circuit, or the like is desirable. The temperature of the developer is preferably 20°C to 30°C, for example. The development time is preferably 20 seconds to 180 seconds. In addition, in order to improve residue removal, the following steps may also be repeated multiple times: shake off the developer every 60 seconds, and then re-supply the developer.

Examples of the alkaline agent used in the developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and hydroxide. Organic basic compounds such as tetrabutylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene. As the developer, it is preferable to use an alkaline aqueous solution in which these alkaline agents are diluted with pure water so that the concentration becomes 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. In addition, an inorganic base may also be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, etc. are preferred. Furthermore, when a developer solution containing such an alkaline aqueous solution is used, it is usually washed (rinsed) with pure water after development.

After development, it is preferable to perform heat treatment (post-baking) after drying. If a plurality of coloring patterns are formed, the steps can be repeated in sequence for each color to produce a cured film. With this, a color filter can be obtained. Post-baking is a heat treatment after development for achieving complete hardening. The heating temperature is preferably, for example, 100°C to 240°C, and more preferably 200°C to 240°C. A heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, and other heating mechanisms can be used to post-bake the developed film by continuous or batch methods in such a manner as described above .

<<Pattern formed by dry etching method (second form)>> The colored composition layer formed on the support can be hardened to form a colored layer, and then, the patterned photoresist layer can be used as A mask is used, and an etching gas is used to pattern the obtained colored layer by dry etching. Specifically, a positive-type or negative-type radiation-sensitive composition is coated on the colored layer and dried to form a photoresist layer. During the formation of the photoresist layer, it is preferable to further perform a pre-baking process. In particular, as the formation process of the photoresist layer, it is desirable to perform a heat treatment after exposure and a heat treatment (post-baking treatment) after development.

As the photoresist layer, for example, a positive-type sensor that senses ultraviolet rays (g-rays, h-rays, i-rays), far-ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays can be preferably used. Radioactive composition. Among the radiations, g-rays, h-rays, and i-rays are preferred, and among them, i-rays are more preferred. Specifically, the positive radiation sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. The positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin utilizes light irradiation with a wavelength of 500 nm or less to decompose the quinonediazide group and generate a carboxyl group. As a result, it changes from an alkali-insoluble state to an alkali Soluble. Since this positive photoresist is remarkably excellent in resolution, it is used in the production of integrated circuits such as integrated circuits (IC) or large scale integrated circuits (Large Scale Integration (LSI)). Examples of the quinonediazide compound include naphthoquinonediazide compounds. Examples of commercially available products include “FHi622BC” (manufactured by Fujifilm Electronic Materials) and the like.

The thickness of the photoresist layer is preferably 0.1 μm to 3 μm, more preferably 0.2 μm to 2.5 μm, and still more preferably 0.3 μm to 2 μm. In addition, the coating method of a positive radiation sensitive composition can be suitably performed using the coating method in the coloring layer already mentioned.

Next, the photoresist layer is exposed and developed, thereby forming a resist pattern (patterned photoresist layer) provided with the resist through-hole group. The formation of the resist pattern is not particularly limited, and it can be suitably performed by optimizing the previously known photolithography technique. The resist through-hole group is provided on the photoresist layer by exposure and development, thereby providing a resist pattern used as an etching mask for subsequent etching on the colored layer.

The exposure of the photoresist layer can be performed by using a predetermined mask pattern, using g-rays, h-rays, i-rays, etc., preferably i-rays to a positive or negative radiation-sensitive linear composition Implement exposure. After the exposure, a developing solution is used to perform a development process, thereby removing the photoresist in combination with the area where the colored pattern is to be formed.

As the developer, any developer can be used as long as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the colored layer. For example, a combination of various solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving a basic compound so that the concentration becomes 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass is suitable. Examples of basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, etc. In addition, when an alkaline aqueous solution is used, the washing treatment is usually performed with water after development.

Next, the resist pattern was used as an etching mask, and patterning was performed by dry etching so as to form a through-hole group on the colored layer. By this, a coloring pattern is formed. The through hole group is preferably provided on the colored layer in a checkerboard pattern, for example. Thereby, the first coloring pattern formed by providing the through-hole group on the coloring layer has a plurality of quadrilateral first coloring pixels in a checkerboard pattern.

As the dry etching, from the viewpoint of forming a pattern cross section closer to a rectangle or the viewpoint of further reducing damage to the support, it is preferably performed in the following form. Preferably, it is a form including the following etching: using a mixed gas of a fluorine-based gas and oxygen (O ₂ ) to perform etching in the first stage until the region (depth) where the support is not exposed; After etching, using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ), the second stage of etching is performed until it is preferably near the area (depth) where the support is exposed; and after the support is exposed Over etching. Hereinafter, the specific method of dry etching, the first-stage etching, the second-stage etching, and the over-etching will be described.

Dry etching is carried out after obtaining the etching conditions in advance by the following method. (1) The etching rate (nm/min) in the first-stage etching and the etching rate (nm/min) in the second-stage etching are calculated separately. (2) The time for etching the desired thickness by the first-stage etching and the time for etching the desired thickness by the second-stage etching are calculated separately. (3) The first-stage etching is performed based on the etching time calculated in (2) above. (4) The second-stage etching is performed based on the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second-stage etching may be performed according to the determined etching time. (5) The over-etching time is calculated with respect to the total time of (3) and (4), and over-etching is performed.

As the mixed gas used in the first-step etching step, from the viewpoint of processing the organic material as the film to be etched into a rectangle, it is preferable to contain a fluorine-based gas and oxygen gas (O ₂ ). In addition, by setting the etching step in the first stage to a form in which the support is not exposed, damage to the support can be avoided. In addition, from the viewpoint of avoiding damage to the support after the etching in the first-step etching step using a mixed gas of fluorine-based gas and oxygen until the support is not exposed, the second-step etching step and excessive The etching step is preferably performed using a mixed gas of nitrogen and oxygen.

It is important that the ratio of the etching amount in the first-step etching step to the etching amount in the second-step etching step is determined so as not to impair the rectangularity formed by the etching process in the first-step etching step. Furthermore, the ratio of the latter in the total etching amount (the sum of the etching amount in the etching step of the first stage and the etching amount in the etching step of the second stage) is preferably greater than 0% and in the range of 50% or less , More preferably 10% to 20%. The etching amount refers to an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

In addition, the etching preferably includes an over-etching process. The over-etching process is preferably performed after setting the over-etching ratio. In addition, the over-etching ratio is preferably calculated based on the time of the initial etching process. The over-etching ratio can be arbitrarily set, but from the viewpoint of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched, it is preferably 30% or less of the etching treatment time in the etching step, and more preferably 5% ～25%, especially good is 10%～15%.

Then, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes the steps of: applying a stripping solution or a solvent to the resist pattern and forming a state in which the resist pattern can be removed; and removing the resist pattern with washing water A step of.

As a step of applying a stripping liquid or a solvent to the resist pattern and forming a state in which the resist pattern can be removed, for example, a stripping liquid or a solvent is applied to at least the resist pattern and stays for a predetermined time To carry out the step of liquid-covered development. The time for allowing the peeling liquid or the solvent to stay is not particularly limited, but it is preferably tens of seconds to several minutes.

In addition, as a step of removing the resist pattern with the cleaning water, for example, a step of removing the resist pattern by spraying cleaning water from a spray nozzle or a spray nozzle to the resist pattern. As the washing water, pure water can be preferably used. In addition, examples of the injection nozzle include an injection nozzle that includes the entire support within its injection range, or a movable injection nozzle that includes the entire support as the movable range. When the spray nozzle is movable, in the step of removing the resist pattern, the cleaning pattern is moved more than twice from the center of the support to the end of the support and sprayed with cleaning water, thereby the resist pattern can be removed more effectively .

The peeling liquid usually contains an organic solvent, and may further contain an inorganic solvent. Examples of organic solvents include: 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether compounds or acetal compounds, 5) ketone compounds or aldehyde compounds, 6) Ester compound, 7) Polyol compound, 8) Carboxylic acid compound or its anhydride compound, 9) Phenolic compound, 10) Nitrogen-containing compound, 11) Sulfur-containing compound, 12) Fluorine-containing compound. The stripping liquid preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The non-cyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanol Ethanolamine, triethanolamine, etc. are preferably monoethanolamine, diethanolamine, triethanolamine, and more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). In addition, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α- Picoline, β-picoline, γ-picoline, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, pyrrolidine , N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine, etc., preferably N-methyl-2-pyrrolidine The ketone and N-ethylmorpholine are more preferably N-Methyl-2-Pyrrolidone (NMP).

The stripping liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and it is more preferable to contain at least one selected from monoethanolamine, diethanolamine, and triethanolamine as the acyclic nitrogen-containing compound, and The cyclic nitrogen-containing compound is at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

When removing with a stripping solution, it is sufficient to remove the resist pattern formed on the colored pattern, and even when deposited matter that is an etching product adheres to the side wall of the colored pattern, it may not be completely removed Sediments. The so-called deposits refer to those formed by depositing and depositing etching products on the side walls of the colored layer.

As the stripping solution, the content of the non-cyclic nitrogen-containing compound is preferably 9 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the stripping solution, and the content of the cyclic nitrogen-containing compound is 65 parts by mass with respect to 100 parts by mass of the stripping solution. Above, below 70 parts by mass. In addition, it is preferable that the peeling liquid is obtained by diluting the mixture of the non-cyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

The method for manufacturing a color filter of the present invention may include, as necessary, steps known as a method for manufacturing a color filter for solid-state imaging elements as steps other than the above. For example, after performing the coloring composition layer forming step, the exposure step, and the pattern forming step, a hardening step of hardening the formed colored pattern by heating and/or exposure may be included as necessary.

In addition, in order to efficiently clean the clogging of the nozzle or piping of the spraying part of the coating device, contamination caused by the adhesion, precipitation, and drying of the coloring composition or pigment in the coating machine, it is preferable to The solvent related to the coloring composition is used as a cleaning liquid. In addition, Japanese Patent Laid-Open No. 7-128867, Japanese Patent Laid-Open No. 7-146562, Japanese Patent Laid-Open No. 8-278637, Japanese Patent Laid-Open No. 2000-273370, Japanese Patent Laid-Open can be suitably used. JP 2006-85140, JP 2006-291191, JP 2007-2101, JP 2007-2102, JP 2007-281523, etc. Washing fluid. Among the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred. These solvents can be used alone or in combination of two or more. When two or more kinds are mixed, it is preferable to mix a solvent having a hydroxyl group and a solvent not having a hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. Particularly preferred is a mixed solvent of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and Propylene Glycol Monomethyl Ether (PGME), and its ratio is 60/40. Furthermore, in order to increase the permeability of the cleaning liquid to contaminants, the surfactant related to the coloring composition of the present invention may be added to the cleaning liquid.

Since the color filter of the present invention is used for the color filter of the present invention, it is excellent in light resistance, color shift property and flatness. The color filter of the present invention can be suitably used for solid-state photographic elements such as CCD and CMOS, and is particularly suitable for high-resolution CCDs or CMOS such as over 1 million pixels. The color filter for a solid-state imaging element of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the coloring pattern (colored pixels) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less. The size (pattern width) of the colored pattern (colored pixels) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

<Solid-state imaging element> The solid-state imaging element of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging element of the present invention is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging element. For example, the following configuration may be mentioned.

The structure is as follows: a plurality of photodiodes constituting a light-receiving area of a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) on a support, and a transfer electrode including polysilicon, etc., on the photodiode And the transfer electrode has a light-shielding film including tungsten or the like that opens only to the light-receiving portion of the photodiode, and the light-shielding film includes nitride formed on the light-shielding film to cover the entire surface of the light-shielding film and the photodiode light-receiving portion A device protective film such as silicon has a color filter for solid-state imaging elements of the present invention on the device protective film. Furthermore, it may have a configuration such as a configuration having a light collecting mechanism (such as a microlens, etc. below) on the device protective layer and under the color filter (near the support), or color filter The optical device has a structure of a light condensing mechanism.

<Image display device> The color filter of the present invention can be used for image display devices such as liquid crystal display devices or organic electroluminescence display devices. Particularly suitable for the use of liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display high-quality images, and the displayed images of the high-quality images have good color tones and excellent display characteristics.

For the definition of the display device or the details of each display device, for example, "Electronic display device (by Shosaki Sasaki, Kogyo Chosakai Publishing (shares) issued in 1990)", "Display device (by Ibuki Shunzo, "Sangyo Tosho (shares) issued in 1989" and so on. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Uchida Ryuo, published by the Industrial Investigation Association (shares) in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

The color filter of the present invention can also be used for a color thin film transistor (Thin Film Transistor, TFT) type liquid crystal display device. The liquid crystal display device of the color TFT method is described in, for example, "Color TFT liquid crystal display (Kyoritsu Publishing (share) issued in 1996). Furthermore, the present invention can also be applied to liquid crystals with a widened viewing angle such as horizontal electric field driving methods such as in-plane switching (IPS), pixel division methods such as multi-domain vertical alignment (MVA), etc. Display device, or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), fringe field switching ( Fringe Field Switching (FFS), and Reflective Optically Compensated Bend (R-OCB), etc. In addition, the color filter in the present invention can also be used in a bright and high-definition color filter array (Color-filter On Array, COA) method. In the liquid crystal display device of the COA method, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer sometimes require the required characteristics of the interlayer insulating film, that is, low dielectric constant and resistance to peeling liquid . Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device with high resolution and excellent long-term durability. Furthermore, in order to satisfy the required characteristics of low dielectric constant, a resin coating may be provided on the color filter layer. Regarding these image display methods, for example, "EL, Plasma Display Panel (PDP), LCD display-the latest trends in technology and market-(Toray Research Center (Toray Research Center) Research and Research Department issued in 2001 )" on page 43, etc.

The liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle protection film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device including these well-known components. About these components, for example, "'94 LCD peripheral materials and chemicals market (Shima Kentaro CMC (shares) issued in 1994)", "2003 LCD related market status and future prospects (Volume 2) "Fuji Chimera Research Institute (shares), issued in 2003)". Regarding the backlight, in "SID (The Society for Information Display) meeting Digest" 1380 (2005) (A. Konno, etc.), or "Monthly Display" It is described on pages 18 to 24 of the December 2005 issue (Shima Kyuyu), pages 25 to 30 of the "Monthly Display" December 2005 issue (Longming Yagi), etc.

If the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with the previously known three-wavelength tube of cold cathode tube, and further, by combining red, green, and blue light emitting diodes (Light Emitting Diode, LED) light source as a backlight, and can provide a liquid crystal display device with high brightness, high color purity and good color reproducibility. [Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples as long as the present invention does not exceed its gist. Furthermore, as long as there is no special explanation in advance, "%" and "parts" are the quality standards.

<Synthesis of xanthene compound (A-xt-1)> [Chem 58]

<<Synthesis of Intermediate 1>> 31 parts of 3,6-dichlorosulfofluorane (DCSF) (manufactured by Chugai Chemicals), 67 parts of 2,6-diisopropylaniline, 17 parts of zinc chloride, cyclic 120 parts of Ding Jie were added to the flask and stirred at an external temperature of 200 degrees for 8 hours. Thereafter, it was left to cool to room temperature, and the reaction was added dropwise to 600 parts of 2 N hydrochloric acid water, and the precipitated crystals were filtered off. After the crystals were dispersed and washed with 600 parts of acetonitrile at 40 degrees, they were filtered and then dried by blowing for 10 hours to obtain 42.5 parts (yield: 82%) of Intermediate 1. <Synthesis of Intermediate 2> 11 parts of Intermediate 1 and 50 parts of phosphorus oxychloride were added to the flask, and stirred at 60°C for 4 hours. After leaving to cool to room temperature, the reaction was added dropwise to 150 parts of ice water and stirred for 30 minutes. The obtained crystals were filtered off and washed with 20 parts of water. Thereafter, the obtained crystals were dissolved in 150 parts of chloroform, and filtered through celite. The filtrate was separated and washed with 100 parts of 5% saline and 100 parts of 15% saline. After the filtrate was dried with sodium sulfate, it was concentrated under reduced pressure to obtain 12.1 parts (yield: 91%) of Intermediate 2. <Synthesis of Intermediate 3> 15 parts of pentafluorobenzenesulfonyl chloride and 300 parts of tetrahydrofuran (THF) were added to the flask, and the internal temperature was cooled to -10°C. 6.8 parts of 28% ammonia water was added dropwise to the reaction liquid so as to maintain the temperature below 0°C. After dropping, after stirring at 0°C for 1 hour, the reaction solution was filtered. The obtained filtrate was concentrated under reduced pressure, and after removing THF, 100 parts of water was added and stirred. The obtained solid was filtered, washed with water, and then blow-dried for 10 hours to obtain 11.7 parts (yield: 84%) of Intermediate 3. <Synthesis of Intermediate 4> 15 parts of Intermediate 3, 4.9 parts of 2-mercaptoethanol, and 100 parts of methanol were added to the flask, and stirred at room temperature. 6.5 parts of triethylamine was added dropwise so that the temperature of the reaction liquid did not exceed 30°C. The reaction solution was stirred at room temperature for 1 hour, and concentrated under reduced pressure, 90 parts of ethyl acetate, 80 parts of saturated saline, and 10 parts of saturated sodium bicarbonate water were added thereto, and a liquid separation operation was performed. After extracting the aqueous layer with 90 parts of ethyl acetate, magnesium sulfate was added to the obtained organic layer. After filtration, the filtrate was concentrated under reduced pressure, and then subjected to air-drying for 10 hours to obtain 17 parts (yield: 92%) of Intermediate 4. <<Synthesis of Intermediate 5>> Add 49 parts of Intermediate 4, 25 parts of 2-isocyanatoethyl acrylate (AOI, manufactured by Showa Denko), 0.2 parts of dibutylhydroxytoluene (BHT), dimethyl 95 parts of acetamide and 0.1 part of Neostann U-600 (manufactured by Nitto Chemical) were stirred at 85°C for 1 hour. Then, 500 parts of ethyl acetate and 500 parts of saturated saline were added thereto and liquid separation operation was performed. After adding sodium sulfate to the obtained organic layer, it was filtered off, and the filtrate was concentrated under reduced pressure. After suspending and washing the obtained solid with 170 parts of chloroform, it was filtered, and then subjected to blow drying, thereby obtaining 60 parts (yield: 84%) of Intermediate 5. <Synthesis of Xanthene Compound (A-xt-1)>> 5 parts of Intermediate 5, 50 parts of dichloromethane, and 3.4 parts of triethylamine were added to the flask and stirred at room temperature. 10.8 parts of Intermediate 2 was added thereto, and stirred at room temperature for 2 hours. After the reaction was completed, 200 parts of chloroform, 500 parts of pure water, and 200 parts of saturated saline were added, and a liquid separation operation was performed. Sodium sulfate was added to the obtained organic layer, and after dehydration, it was filtered off, and the filtrate was concentrated under reduced pressure. The obtained solid was dissolved in chloroform, and purified by column chromatography using a chloroform/ethyl acetate solvent, thereby obtaining 12.5 parts (yield: 86%) of A-xt-1.

＜Xanthene compound (A-xt-2), Xanthene compound (A-xt-4), Xanthene compound (A-xt-6), Xanthene compound (A-xt-7), Xanthene compound (A -xt-9), xanthene compound (A-xt-12), xanthene compound (A-xt-15) synthesis examples> Xanthene compound (A-xt-1) was synthesized following the synthesis of the xanthene compound (A-xt-1) ( A-xt-2), Xanthene compound (A-xt-4), Xanthene compound (A-xt-6), Xanthene compound (A-xt-7), Xanthene compound (A-xt-9) , Xanthene compound (A-xt-12), Xanthene compound (A-xt-15).

<Synthesis of pigment polymer represented by general formula (1)> [Synthesis of pigment polymer S-1] [Chem 59]

Under a nitrogen gas flow, 1.0 part of the polyfunctional thiol (the compound of the structure (SH-1), manufactured by SC Organic Chemical Industry (Co., Ltd.)), 13.7 parts of the xanthene compound (A-xt-1), methyl A mixed solution of 2.1 parts of acrylic acid (MAA) and 9.0 parts of cyclohexanone was heated to 80°C. To this, 0.254 parts of 2,2'-azobis(isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemicals] was added, followed by heating and stirring at 80°C for 2 hours. After further adding 0.254 parts of V-601, the mixture was heated and stirred at 80°C for 2 hours, and further heated and stirred at 90°C for 2 hours. After cooling to room temperature, 30.7 parts of cyclohexanone, 0.32 parts of tetrabutylammonium bromide (TBAB), and 1.8 parts of glycidyl methacrylate (GMA) were added, and the mixture was heated and stirred at 80°C for 18 hours. After cooling to room temperature, the reaction solution was added dropwise to a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate to perform reprecipitation to obtain pigment polymer S-1. The weight average molecular weight (in terms of polystyrene) of the pigment polymer S-1 was 14,500, and the acid value was 40 mgKOH/g by titration using 0.1 N sodium hydroxide aqueous solution. In addition, the number of repeating units having a pigment structure of the polymer chain Q was calculated to be 4.5 on average by NMR (nuclear magnetic resonance) measurement. In addition, dissolve in tetrahydrofuran (THF) to prepare a solution containing 0.01 mg/ml of pigment multimer S-1 (concentration adjusted so that the maximum absorbance becomes 1.0), using a unit with an optical path length of 1 cm The absorbance of the solution at 25°C was measured. As a result, the maximum absorption wavelength (λmax) was 535 nm, and the specific absorption of the maximum absorption wavelength (λmax) was 44.

[Synthesis of Dye Polymer S-2 to Dye Polymer S-52] In addition to changing the polyfunctional thiol, the types and amounts of various monomers, the amount of V-601, the amount of GMA, and the amount of TBAB to the following In addition to the above description, the pigment polymer S-2 to the pigment polymer S-52 were obtained in accordance with the synthesis method of the pigment polymer S-1.

<Measurement of specific absorbance> Dissolve each pigment polymer in tetrahydrofuran (THF) and adjust the concentration to a concentration at which the maximum absorbance at a wavelength of 400 nm to 800 nm becomes 1.0, use a unit with an optical path length of 1 cm, and The absorbance of this solution at 25°C was calculated according to the following formula (Aλ). E=A/(c×l)... (Aλ) In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength within 400 nm to 800 nm, and A represents the maximum absorption within 400 nm to 800 nm The absorbance at the absorption wavelength, l represents the unit length expressed in cm, and c represents the concentration of the pigment polymer in the solution expressed in mg/ml.

[Table 1]

[化61]

[化62]

[化63]

The types of monomers described in the table are shown below. [化60]

[化61]

[化62]

[化63]

Comparative pigment (S'-1), comparative pigment (S'-2), comparative pigment (S'-3): the following structure [Chem64]

依據日本專利特開2000-162429號公報中所記載的方法來合成三芳基甲烷化合物（A-tp-101）。 將三芳基甲烷化合物（A-tp-101）（15 g）、甲基丙烯酸羥基乙酯（10 g）、甲基丙烯酸（5.5 g）、及偶氮雙異丁腈（5 g）添加至N-乙基吡咯啶酮（70 g）中，並於室溫下攪拌30分鐘來進行溶解（滴加用聚合溶液）。 另外，將三芳基甲烷化合物（A-tp-101）（15 g）、甲基丙烯酸羥基乙酯（10 g）、及甲基丙烯酸（5.5 g）加入至容器中來進行溶解，並於80℃下進行攪拌。歷時3小時向其中滴加所製備的滴加用聚合溶液，攪拌1小時後，添加偶氮異丁腈（2.5 g），進而反應2小時後停止。冷卻至室溫為止後，將溶媒餾去，而獲得比較色素3。比較色素3的重量平均分子量（Mw）為18000，藉由使用0.1 N氫氧化鈉水溶液的滴定，酸價為1.81 mgKOH/g。(Comparative synthesis of pigment (S'-3)) [Chem 65]

The triarylmethane compound (A-tp-101) was synthesized according to the method described in Japanese Patent Laid-Open No. 2000-162429. Add triarylmethane compound (A-tp-101) (15 g), hydroxyethyl methacrylate (10 g), methacrylic acid (5.5 g), and azobisisobutyronitrile (5 g) to N -Dissolve in ethylpyrrolidone (70 g) and stir at room temperature for 30 minutes (polymerization solution for dropping). In addition, the triarylmethane compound (A-tp-101) (15 g), hydroxyethyl methacrylate (10 g), and methacrylic acid (5.5 g) were added to the vessel for dissolution and at 80°C Stir under. The prepared polymerization solution for dropping was added dropwise thereto over 3 hours, and after stirring for 1 hour, azoisobutyronitrile (2.5 g) was added, and the reaction was stopped after 2 hours. After cooling to room temperature, the solvent was distilled off to obtain Comparative Pigment 3. The weight average molecular weight (Mw) of Comparative Pigment 3 was 18000, and the acid value was 1.81 mgKOH/g by titration using 0.1 N sodium hydroxide aqueous solution.

<Example 1> 1. Preparation of resist solution After mixing and dissolving the components of the following composition, filtration was performed with a 0.45 μm nylon filter, thereby preparing a resist solution for an undercoat layer. Composition of resist liquid for undercoat layer·Solvent: 19.20 parts of propylene glycol monomethyl ether acetate·Solvent: 36.67 parts of ethyl lactate·Alkali-soluble resin: benzyl methacrylate/methacrylic acid/methacrylic acid-2- Hydroxyethyl copolymer (Molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) in 40% PGMEA solution 30.51 parts · Polymerizable compound: dipentaerythritol hexaacrylate (Kayarad (KAYARAD) DPHA (manufactured by Nippon Kayaku) 12.20 parts · Polymerization inhibitor: 0.0061 parts of p-methoxyphenol · Fluorine-based surfactant: F-475, 0.83 parts manufactured by Di Aisheng (share) · Photopolymerization start Agent: Trihalomethyltriazine-based photopolymerization initiator (TAZ-107, manufactured by Midori Kagaku Chemical Company) 0.586 parts

2. Fabrication of a silicon wafer substrate with an undercoat layer. A 6-inch silicon wafer was heated at 200°C for 30 minutes in an oven. Then, the resist liquid for the undercoat layer was applied on the silicon wafer with a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220° C. for 1 hour to form an undercoat layer, thereby obtaining Undercoat silicon wafer substrate.

3. Preparation of coloring composition 3-1. Preparation of blue pigment dispersion liquid (preparation of pigment dispersion liquid P1 (CI pigment blue 15:6 dispersion liquid)) Pigment dispersion liquid P1 (CI pigment blue 15: 6 dispersion). That is, using a beads mill (zirconia beads, diameter 0.3 mm), the CI pigment blue 15:6 (blue pigment; hereinafter also referred to as "PB15:6") 19.4 parts by mass (average once The particle size is 55 nm), and 2.95 parts by mass of dispersion resin BY-161 (manufactured by BYK Chemical Co., Ltd.) and 2.95 parts by mass in terms of solid content of alkali-soluble resin J1 (copolymerization of benzyl methacrylate/methacrylic acid) Mixture of 30% PGMEA solution) (the solution is 9.93 parts by mass) and 165.3 parts by mass of PGMEA, and the mixture is mixed and dispersed for 3 hours. Thereafter, a high-pressure dispersing machine NANO-3000-10 (manufactured by Japan BEE Co., Ltd.) with a decompression mechanism was further used to carry out dispersion treatment at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . This dispersion process was repeated 10 times to obtain a CI Pigment Blue 15:6 dispersion liquid as a pigment dispersion liquid. With respect to the obtained CI Pigment Blue 15:6 dispersion liquid, the average primary particle diameter of the pigment was measured by dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and the result was 24 nm.

Alkali soluble resin J1 [Chem 66]

3-2. Preparation of colored composition The following components are mixed, dispersed and dissolved, and filtered with a 0.45 μm nylon filter to obtain a colored composition. · Organic solvent (cyclohexanone): 17.12 parts · Alkali soluble resin 1 (J1 below): 1.23 parts (solid content 0.37 parts, solid content concentration 30%) · Alkali soluble resin 2 (Acrycure)- RD-F8 (manufactured by Japan Catalyst Company)): 0.23 parts • Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.975 parts • Pigment polymer cyclohexanone solution (solid content Concentration: 12.3%): 24.57 parts · Pigment Dispersion Liquid P1 (CI Pigment Blue 15:6 dispersion liquid, PGMEA solution, solid content concentration is 12.8%): 51.40 parts · Polymeric Compound Z-1 (ethoxylated modification) Dipentaerythritol hexaacrylate, NK ESTER A-DPH-12E (manufactured by Shin Nakamura Chemical Co., Ltd.): 1.96 parts · Polymerization inhibitor (p-methoxyphenol): 0.0007 part · Fluorine-based surfactant (manufactured by Di Aisheng Company) F475, 1% PGMEA solution): 2.50 parts

4. Production of color filter (coloring pattern) 4-1: Production of color filter using coloring composition by photolithography method The coloring composition prepared above is applied to the belt prepared above A colored layer (coating film) is formed on the undercoat layer of the silicon wafer with the undercoat layer. Then, using a 100° C. hot plate, a 120-second heat treatment (pre-baking) was performed so that the dried film thickness of the coated film became 1 μm. Then, using the i-ray stepping exposure device FPA-3000i5+ (manufactured by Canon), at a wavelength of 365 nm, the transmission pattern was masked with a square island pattern of 1.0 μm on each side, to Exposure is performed at an exposure amount of 50 mJ/cm ² to 1200 mJ/cm ² . After that, the silicon wafer substrate on which the irradiated coating film was formed was placed on a horizontal rotary table of a rotary and shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), using CD-2000 (Fuji Film electronic materials (manufactured by Co., Ltd.) was developed at 23°C for 60 seconds with over-liquid development, and a colored pattern was formed on the undercoat layer of the silicon wafer with the undercoat layer. The silicon wafer with the colored pattern formed is fixed on a horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at 50 rpm using a rotating device, and from above the center of rotation, the nozzle is sprayed Pure water is supplied in a shower to perform the rinse treatment. After that, it was spray-dried and post-baked at 200°C for 300 seconds using a hot plate to obtain a color pattern (color filter) with a thickness of 1 μm on the silicon wafer. In the above manner, a colored patterned silicon wafer in which a colored pattern (color filter) is provided on the undercoat layer of the silicon wafer with an undercoat layer is obtained. After that, the length of the colored pattern was measured using Scanning Electron Microscope (SEM) "S-9260A" (manufactured by Hitachi High-Technologies (shares)). Evaluation of the development residue was performed using a coloring pattern whose pattern size became an exposure amount of 1.0 μm.

<Evaluation of development residue> Using a scanning electron microscope, the outside of the formation area of the coloring pattern (unexposed portion) in the silicon wafer was observed at a magnification of 30,000 times, and evaluation was performed according to the following evaluation criteria. A: No residue was observed at all outside the colored pattern formation area (unexposed part). B: Outside the colored pattern formation area (unexposed part), residues were slightly confirmed, but they were of a degree that there was no practical problem. C: Residue was confirmed outside the colored pattern formation area (unexposed part). The development conditions were changed from liquid-covered development at 23° C. for 60 seconds to liquid-covered development at 23° C. for 180 seconds, thereby becoming practically problem-free. D: Residues were clearly recognized outside the colored pattern formation area (unexposed part).

<Evaluation of color shiftability>> The absorbance (absorbance A) of the coloring pattern in each color filter was measured with MCPD-3000 (manufactured by Otsuka Electronics). Apply the CT-2000L solution (manufactured by Fuji Film Electronic Materials (Co., Ltd.); transparent base agent) so that the dry film thickness becomes 1 μm, and dry the colored pattern forming surface of the color filter to form a transparent film. , Heat treatment at 280°C for 5 minutes. After the heating was completed, the absorbance (absorbance B) of the transparent film adjacent to the colored pattern was measured using MCPD-3000 (manufactured by Otsuka Electronics). With respect to the value of the absorbance B of the obtained transparent film, the ratio [%] [the following (formula A)] to the value of the absorbance A of the coloring pattern measured before heating was calculated. This is used as an index for evaluating the color shift toward the adjacent pixel (pixel). (Formula A) Color shift (%) = (absorbance B/absorbance A) × 100 A: less than 1% B: more than 1%, less than 3% C: more than 3%, less than 10% D: more than 10%

<Evaluation of light resistance>> Using a spin coater (Mikasa (manufactured by Mikasa)), the color-forming photosensitive composition prepared above was coated on a glass substrate to form a coating film. Then, heat treatment (pre-baking) was performed for 120 seconds using a 100° C. hot plate so that the dried film thickness of the coating film became 0.6 μm. Then, heating was performed at 200° C. for 5 minutes, and the coating film was cured to form a colored layer. Use a lightfastness test device (SX-75 manufactured by Suga Test Instrument), a black panel temperature of 63°C, a quartz internal filter, a 275 nm cut-off external filter, and an illumination of 75 mw/m ² (300 nm to 400 nm) and a humidity of 50%, the glass substrate on which the colored layer was formed was subjected to a light resistance test for 10 hours. The color difference (ΔE*ab) before and after the light resistance test was measured using a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). Based on the measured color difference (ΔE*ab), light resistance was evaluated according to the following evaluation criteria. It can be said that the smaller the value, the better the light resistance. The evaluation results are shown in the following table. A and B are the level of no problem in actual use.

<Evaluation criteria> A: ΔE*ab is 3 or less B: ΔE*ab is greater than 3 and 5 or less C: ΔE*ab is greater than 5 and 10 or less D: ΔE*ab is greater than 10

<<Evaluation of flatness>> Using a spin coater (Mikasa Co., Ltd.), 1.0 mL of the color composition prepared above was coated on a 4-inch silicon wafer to form a coating film. Then, a colored layer was formed by performing a heat treatment (pre-baking) for 120 seconds using a 100°C hot plate so that the dry film thickness at the center of the coating film became 0.60 μm. An optical film thickness meter (Filmetrics (share) F20) was used to measure the film thickness of the colored layer. It can be said that the smaller the difference between the thinnest part (central part) and the thickest part (peripheral part), the better. The evaluation results are shown in the following table. A and B are the level of no problem in actual use.

<Evaluation Criteria> A: The difference in film thickness is 0.02 μm or less B: The difference in film thickness is more than 0.02 μm and 0.05 μm or less C: The difference in film thickness is more than 0.05 μm.

<Example 2 to Example 52, Comparative Example 1 to Comparative Example 3>

In "3-2. Preparation of coloring composition" in Example 1, the pigment dispersion liquid, the pigment polymer (pigment), the photopolymerization initiator, the alkali-soluble resin, and the polymerizable compound were changed as shown in the following table. Except for this, the coloring composition was prepared in the same manner as in Example 1, and the developing residue, color shift, light resistance, and flatness were evaluated in the same manner as in Example 1. In addition, in Comparative Examples 1 to 3, the comparative dyes S′-1 to Sd-3 were used as dye polymers.

[Table 2]

Based on the results, the coloring compositions of Examples 1 to 52 are excellent in color shift, light resistance, and flatness. Furthermore, there are very few development residues and excellent developability. On the other hand, any of the color shift properties and flatness of Comparative Examples 1 to 3 is poor.

<Example 53, Example 54> The following components were mixed, dispersed and dissolved, and filtered through a 0.45 μm nylon filter to obtain a colored composition. Then, using a spin coater, the obtained coloring composition was coated on a 7.5 cm×7.5 cm glass substrate so that the film thickness became 0.5 μm, and heated at 200° C. for 5 minutes using a hot plate. Then, the coating film is cured to produce a colored layer. The film thickness of this colored layer is 0.5 μm. Then, a positive photoresist "FHi622BC" (manufactured by Fuji Film Electronic Materials Co., Ltd.) was applied, and pre-baking treatment was performed at 90°C for 1 minute to form a photoresist layer with a film thickness of 0.8 μm. Then, using an i-ray stepper (manufactured by Canon Co., Ltd.), the photoresist layer was pattern-exposed with an exposure of 350 mJ/cm ² , and then the temperature of the photoresist layer or the ambient temperature became 90°C. Heat treatment is carried out for 1 minute. After that, a developing process of "FHD-5" (manufactured by Fuji Film Electronic Materials Co., Ltd.) was performed for 1 minute, and then a post-baking process was performed at 110°C for 1 minute to form a resist pattern. The size of the resist pattern is formed with 1.0 μm on one side in consideration of the difference in etching conversion (reduction in pattern width due to etching). Then, the glass substrate with the photoresist layer formed was attached to an 8-inch silicon wafer, using a dry etching device (U-621, manufactured by Hitachi Advanced Technologies Co., Ltd.), and the radio frequency (Radio Frequency, RF) power was set to 800 W, the antenna bias is set to 400 W, the wafer bias is set to 200 W, the internal pressure of the reaction chamber is set to 4.0 Pa, the substrate temperature is set to 50°C, and the gas type and flow rate of the mixed gas are set to CF ₄ : 80 mL/min, O ₂ : 40 mL/min, Ar: 800 mL/min., and the first-stage etching treatment of 80 seconds was performed. Then, in the same etching reaction chamber, the RF power was set to 600 W, the antenna bias was set to 100 W, the wafer bias was set to 250 W, the internal pressure of the reaction chamber was set to 2.0 Pa, and the substrate temperature Set to 50°C, and set the gas type and flow rate of the mixed gas to N ₂ : 500 mL/min, O ₂ : 50 mL/min, Ar: 500 mL/min (N ₂ /O ₂ /Ar=10/1/ 10) The second-stage etching process of 28 seconds is carried out. After dry etching under the above conditions, a resist stripping solution "MS230C" (manufactured by Fuji Film Electronic Materials Co., Ltd.) was used to perform a stripping treatment at 50°C for 120 seconds to remove the resist to form a colored pattern. Furthermore, washing with pure water and spin drying were performed, and then, dehydration baking treatment was performed at 100°C for 2 minutes. In the above manner, a color filter is obtained. With respect to the obtained color filter, color shift properties, light resistance, and flatness were evaluated in the same manner as in Example 1. <Composition of coloring composition> · Organic solvent (cyclohexanone): 17.12 parts · Epoxy resin JER1031S (manufactured by Mitsubishi Chemical Corporation), epoxy equivalent: 180-220 (g/eq.): 4.395 parts · Pigment Multimer cyclohexanone solution (solid content concentration 12.3%): 24.57 parts·Pigment dispersion liquid (refer to the following table): 51.40 parts·Polymerization inhibitor (p-methoxyphenol): 0.0007 parts·Fluorine interface Active agent (F475, 1% PGMEA solution manufactured by Di Aisheng): 2.50 parts

[table 3]

Based on the above results, the coloring compositions of Example 53 and Example 54 are excellent in color shift properties, light resistance, and flatness.

The abbreviations of the compounds described in the table are as follows.

Photopolymerization initiator: the following structure [Chem 67]

Alkali soluble resin: The following structure [Chemical 68]

Polymeric compound Z-1: Ethoxylated modified dipentaerythritol hexaacrylate, NK ESTER A-DPH-12E (manufactured by Shin Nakamura Chemical Company) Z-2: Dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) Z-3: ethoxylated (4) pentaerythritol tetraacrylate, SR494 (manufactured by Sadoran) Z-4: ethoxylated (3) trimethylolpropane triacrylic acid Ester, SR454 (manufactured by Sadoran) Z-5: ethoxylated (6) trimethylolpropane triacrylate, SR499 (manufactured by Sadoran) Z-6: Kayarad (DPCA) -60 (manufactured by Nippon Kayaku Co., Ltd.) Z-7: tris(2-hydroxyethyl) isocyanurate triacrylate, SR368 (manufactured by Sadoran)

Mw=20000，x/y=50/50（質量比），n=20，酸價=100 mgKOH/g 顏料分散液P3（C.I.顏料藍15：6分散液）： 於顏料分散液P1的製備中，使用下述分散樹脂D2來代替分散樹脂BY-161，除此以外，藉由相同的操作來製備顏料分散液P3。 [化70]

Mw=20000，x/y=15/85（質量比），n=20，酸價=100 mgKOH/g 顏料分散液P4（C.I.顏料紫23分散液）： 於顏料分散液P1的製備中，使用C.I.顏料紫23來代替PB15：6作為顏料，除此以外，以與顏料分散液P1的製備相同的方式製備顏料分散液P4。 顏料分散液P5（C.I.顏料紅254分散液）： 於顏料分散液P1的製備中，使用C.I.顏料紅254來代替PB15：6作為顏料，除此以外，以與顏料分散液P1的製備相同的方式製備顏料分散液P5。 顏料分散液P6（C.I.顏料綠58分散液）： 於顏料分散液P1的製備中，使用C.I.顏料綠58來代替PB15：6作為顏料，除此以外，以與顏料分散液P1的製備相同的方式製備顏料分散液P6。 顏料分散液P7（C.I.顏料黃139分散液）： 於顏料分散液P1的製備中，使用C.I.顏料黃139來代替PB15：6作為顏料，除此以外，以與顏料分散液P1的製備相同的方式製備顏料分散液P7。Pigment Dispersion Pigment Dispersion P2 (CI Pigment Blue 15:6 Dispersion): In the preparation of Pigment Dispersion P1, the following dispersing resin D1 was used instead of dispersing resin BY-161, except that the same operation To prepare pigment dispersion P2. [化69]

Mw=20000, x/y=50/50 (mass ratio), n=20, acid value=100 mgKOH/g Pigment dispersion P3 (CI Pigment Blue 15:6 dispersion): In the preparation of pigment dispersion P1 The pigment dispersion liquid P3 was prepared by the same operation except that the following dispersion resin D2 was used instead of the dispersion resin BY-161. [化70]

Mw=20000, x/y=15/85 (mass ratio), n=20, acid value=100 mgKOH/g pigment dispersion P4 (CI pigment violet 23 dispersion): used in the preparation of pigment dispersion P1 In addition to CI Pigment Violet 23 instead of PB15:6 as a pigment, pigment dispersion liquid P4 was prepared in the same manner as the preparation of pigment dispersion liquid P1. Pigment Dispersion P5 (CI Pigment Red 254 Dispersion): In the preparation of Pigment Dispersion P1, CI Pigment Red 254 was used instead of PB15:6 as the pigment, except that it was the same as the preparation of Pigment Dispersion P1 Preparation of pigment dispersion P5. Pigment Dispersion P6 (CI Pigment Green 58 Dispersion): In the preparation of Pigment Dispersion P1, CI Pigment Green 58 was used instead of PB15:6 as the pigment, except that it was the same as the preparation of Pigment Dispersion P1 Preparation of pigment dispersion P6. Pigment Dispersion P7 (CI Pigment Yellow 139 Dispersion): In the preparation of Pigment Dispersion P1, CI Pigment Yellow 139 was used instead of PB15:6 as the pigment, except that it was the same as the preparation of Pigment Dispersion P1 Preparation of pigment dispersion P7.

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Claims (17)

A coloring composition including a pigment polymer represented by the general formula (1) and a polymerizable compound; P-(Q) _n ... (1) In the general formula (1), P represents derived from a polyol N-valent linking group, Q represents a polymer chain containing a repeating unit represented by the general formula (a1-1), and the average value of the number of n Q repeating units represented by the general formula (a1-1) is 2~20, n represents an integer of 3~10,

In the general formula (a1-1), Q ¹ represents a trivalent linking group, and L ¹ represents a single bond, an alkylene group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group, and -CH =CH-, -O-, -S-, -C(=O)-, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -, or A linking group formed by linking two or more of these, R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and D ¹ represents a source derived from a triarylmethane dye, a xanthene dye, an anthraquinone dye, The pigment structure of the cyanine pigment, squarylium salt pigment, quinophthalone pigment, phthalocyanine pigment, subphthalocyanine pigment, azo pigment and dipyrromethene pigment, "*" represents the main chain Combining keys. The coloring composition as described in item 1 of the patent application, wherein the pigment polymer is represented by the general formula (2);

In the general formula (2), A ¹ represents an n-valent linking group derived from a polyol, and B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-, R represents a hydrogen atom, alkyl group or aryl group, C ¹ represents a single bond, alkylene group, aryl group or oxyalkylene group, S represents a sulfur atom, Q Has the same meaning as the repeating unit represented by the general formula (a1-1), and n represents an integer of 3-10. The coloring composition as described in item 2 of the scope of the patent application, wherein the A ¹ is one or more selected from aliphatic hydrocarbon groups, aromatic ring groups and heterocyclic groups which may have an oxygen atom in the main chain Combined base. The coloring composition as described in any one of claims 1 to 3, wherein the pigment polymer has a maximum absorption wavelength in the range of 400 nm to 800 nm The specific absorbance represented by the following formula (Aλ) in is 5 or more, and the average value of the number of repeating units represented by the general formula (a1-1) of n Q is 2 to 7.3; E=A /(c×1)... (Aλ) In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength within 400 nm to 800 nm, A represents the absorbance at the maximum absorption wavelength within 400 nm to 800 nm, and l represents the unit The unit length is expressed in cm, and c is the concentration of the pigment polymer in the solution expressed in mg/ml. The coloring composition according to any one of claims 1 to 3, wherein the pigment polymer contains 1% by mass to 50% by mass relative to the total solid content of the coloring composition. The coloring composition according to any one of claims 1 to 3, wherein the pigment polymer is a compound represented by the general formula (3), and has a compound derived from a triaryl group Methane pigment, xanthene pigment, anthraquinone pigment, cyanine pigment, squarylium salt pigment, quinophthalone pigment, phthalocyanine pigment, subphthalocyanine pigment, azo pigment and dipyrromethene pigment Pigment structure and radical polymerizable group compound obtained by radical polymerization, P ^0- (SH) _n … (3) In the general formula (3), P ⁰ represents an n-valent linking group derived from a polyol , SH represents a thiol group, and n represents an integer of 3-10. The coloring composition as described in any one of claims 1 to 3, further includes pigments other than the pigment polymer. The coloring composition as described in any one of claims 1 to 3, further includes a photopolymerization initiator. The coloring composition according to any one of claims 1 to 3, wherein the Q contains one or more kinds selected from a repeating unit having an acid group and a repeating unit having a polymerizable group. The coloring composition as described in any one of claims 1 to 3, wherein Q is selected from (meth)acrylic resin, styrene resin, and (meth)acrylic acid/benzene One of vinyl resins. A color filter formed using the coloring composition as described in any one of claims 1 to 10. A pattern forming method, comprising: applying a coloring composition as described in any one of claims 1 to 10 to a support to form a coloring composition layer; applying the coloring composition layer A step of exposing in a pattern; and a step of developing and removing the unexposed portion of the colored composition layer exposed in a pattern to form a colored pattern. A pattern forming method, comprising: applying a coloring composition as described in any one of claims 1 to 10 to a support to form a coloring composition layer, and hardening it to form a coloring layer Step; forming a photoresist layer on the colored layer; step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and applying the resist pattern The step of dry etching the colored layer to form a colored pattern as an etching mask. A method for manufacturing a color filter, which includes the pattern forming method as described in item 12 or item 13 of the patent application. A solid-state imaging element including the color filter as described in item 11 of the patent application scope. An image display device including the color filter as described in item 11 of the patent application scope. A method for producing a pigment polymer, which is a method for producing a pigment polymer represented by the general formula (1), and includes a compound represented by the general formula (3) and a compound derived from a triaryl group Methane pigment, xanthene pigment, anthraquinone pigment, cyanine pigment, squarylium salt pigment, quinophthalone pigment, phthalocyanine pigment, subphthalocyanine pigment, azo pigment and dipyrromethene pigment The compound of the pigment structure and the radical polymerizable group undergoes radical polymerization. P ⁰ -(SH) _n … (3) In the general formula (3), P ⁰ represents an n-valent linking group derived from a polyol, and SH represents Thiol group, n represents an integer of 3 to 10, P-(Q) _n … (1) In the general formula (1), P represents an n-valent linking group derived from a polyol, and Q represents a general formula (a1) -1) The polymer chain of the repeating unit represented by n, the average value of the number of repeating units represented by the general formula (a1-1) of n Q is 2 to 20, n represents an integer of 3 to 10,

In the general formula (a1-1), Q ¹ represents a trivalent linking group, and L ¹ represents a single bond, an alkylene group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group, and -CH =CH-, -O-, -S-, -C(=O)-, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -, or A linking group formed by linking two or more of these, R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and D ¹ represents a source derived from a triarylmethane dye, a xanthene dye, an anthraquinone dye, The pigment structure of the cyanine pigment, squarylium salt pigment, quinophthalone pigment, phthalocyanine pigment, subphthalocyanine pigment, azo pigment and dipyrromethene pigment, "*" represents the main chain Combining keys.