KR101876278B1

KR101876278B1 - Coloring composition, cured film, color filter, method for manufacturing color filter, solid-state image pickup device, and image display device

Info

Publication number: KR101876278B1
Application number: KR1020167002343A
Authority: KR
Inventors: 요시노리 타구치; 카즈야 오오타; 나오츠구 무로; 테츠야 와타나베; 유우시 카네코; 준이치 이토; 스구루 사메지마
Original assignee: 후지필름 가부시키가이샤
Priority date: 2013-08-01
Filing date: 2014-07-30
Publication date: 2018-07-09
Also published as: JP6147134B2; KR20160027056A; TWI632204B; TW201506093A; JP2015030783A; WO2015016243A1

Abstract

A coloring composition, a cured film, a color filter, a method for producing a color filter, a solid-state image pickup device and an image display device which are difficult to generate foreign matter when placed under a low temperature environment for a long time.
A coloring composition comprising (A) a pigment multimer and (B) a solvent, wherein (A) the pigment multimer has a partial structure and an anion site derived from a xanthate dye having a cation moiety, Ion concentration is 0.1 to 10 ppm.

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring composition, a cured film, a color filter, a method of manufacturing a color filter, a solid-state image pickup device and an image display device.

The present invention relates to a coloring composition and a cured film using the same. The present invention also relates to a color filter having a cured film, a method of manufacturing a color filter, a solid-state image pickup device having a color filter, and an image display apparatus.

As a method for producing a color filter for use in a liquid crystal display device or a solid-state image pickup device, there is a pigment dispersion method. As the pigment dispersion method, a color photosensitive composition in which pigments are dispersed in various photosensitive compositions is used. Thereby manufacturing a color filter. That is, the colored composition is coated on a substrate by using a spin coater, a roll coater, or the like, followed by drying to form a coated film, and the coated film is exposed by pattern exposure to obtain a colored pixel. By repeating this operation for the desired color minutes, a color filter is produced.

The above method is stable against light and heat in terms of using pigments and ensures sufficient positional precision in that patterning is carried out by photolithography and is widely used as a suitable method for producing color filters for color displays and the like Has come.

Patent Document 1 discloses the use of a colored photosensitive composition including a dye and a pigment in the production of a color filter. Patent Document 2 discloses improving the developability by using a dye multimer containing a xanthene skeleton as a partial structure of a dye moiety. Patent Document 2 also discloses a combination of a cation site and an anion site in a dye multimer.

Patent Document 1: JP-A-2008-268242 Patent Document 2: JP-A-2012-32754

Here, when a color filter formed by using a composition containing a multimeric dye having an anion site and a partial structure derived from a xanthine dye having a cation site is placed for a long time under a low-temperature environment, foreign matter tends to be generated .

An object of the present invention is to provide a colored composition which is difficult to generate foreign matter when placed under a low temperature environment for a long time.

The present inventors have found that by adjusting at least one of a sodium ion concentration and a potassium ion concentration to a specific range in a composition comprising a dye multimer having a partial structure derived from a xanthine dye having a cation site and an anion site, I found that I could solve it.

More specifically, the above-mentioned problem is solved by the following means <1>, preferably by <2> to <14>.

&Lt; 1 > A coloring composition comprising (A) a pigment multimer and (B) a solvent,

(A) a dye multimer having a partial structure derived from a xanthine dye having a cation moiety and an anion moiety,

Wherein at least one of a sodium ion concentration and a potassium ion concentration in the coloring composition is 0.1 to 10 ppm.

<2> The coloring composition according to <1>, wherein the toluene concentration in the coloring composition is 1 to 13 ppm.

<3> The coloring composition according to <1> or <2>, wherein the water content in the coloring composition is 0.1 to 5% by mass.

&Lt; 4 > The coloring composition according to any one of < 1 > to < 3 >, wherein the anion site is an anion site of a low nucleus.

&Lt; 5 > A coloring composition according to any one of <1> to <4>, further comprising a pigment.

<6> The coloring composition according to any one of <1> to <5>, which further comprises a photopolymerization initiator.

<7> The coloring composition according to any one of <1> to <6>, which further comprises a curable compound.

<8> The coloring composition according to any one of <1> to <7>, wherein at least one of the sodium ion concentration and the potassium ion concentration in the coloring composition is 3-7 ppm.

<9> The coloring composition according to any one of <1> to <8>, which is for forming a coloring layer of a color filter.

<10> A cured film obtained by curing a colored composition according to any one of <1> to <9>.

<11> A process for producing a colored composition, comprising the steps of: applying a coloring composition according to any one of <1> to <9> on a support to form a coloring composition layer; exposing the coloring composition layer to a pattern; And forming a coloring pattern on the color filter.

&Lt; 12 > A process for producing a coloring composition comprising the steps of applying a coloring composition according to any one of < 1 > to < 9 &

A step of forming a photoresist layer on the colored layer,

A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and

And dry etching the colored layer using the resist pattern as an etching mask.

<13> A color filter having a cured film according to <10> or a color filter manufactured by the method of manufacturing a color filter according to <11> or <12>.

&Lt; 14 > A solid-state image pickup device or image display device having a color filter according to < 13 >.

According to the present invention, it has become possible to provide a colored composition which is difficult to generate foreign matter when it is placed for a long time under a low-temperature environment.

Descriptions of the constituent elements in the present invention described below are based on the exemplary embodiments of the present invention, but the present invention is not limited to those embodiments.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term " radiation " in this specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray. In the present invention, light means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle lines such as electron beams and ion beams .

In the present specification, the numerical range indicated by using " ~ " means a range including numerical values written before and after "~" as a lower limit value and an upper limit value.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.

In the present specification, the term " (meth) acrylate " refers to both or either acrylate and methacrylate, and " (meth) acrylate " refers to both acrylate and methacrylate, The term " (meth) acryloyl " refers to both acryloyl and methacryloyl.

Also, in this specification, the terms " monomer " and " monomer " are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr indicates a propyl group, Bu indicates a butyl group, and Ph indicates a phenyl group.

In this specification, the term " process " is included in this term as well as an independent process, even if it is impossible to clearly distinguish it from another process, even if the desired action of the process is achieved.

The coloring composition of the present invention (hereinafter also referred to as a composition of the present invention) is a coloring composition containing (A) a pigment multimer and (B) a solvent, wherein (A) the pigment multimer is derived from a xanthine dye having a cationic moiety (Hereinafter sometimes referred to as a " dye structure ") and an anion site, and at least one of a sodium ion concentration and a potassium ion concentration in the composition of the present invention is 0.1 to 10 ppm.

According to the present invention, it is possible to provide a colored composition which is less liable to generate foreign matter when it is left in a low temperature environment (for example, -30 to 0 占 폚) for a long period of time (for example, one month or more).

This mechanism is presumed, however, by controlling at least one of the sodium ion concentration and the potassium ion concentration to 10 ppm or less, the ion exchange reaction of at least one of the cation in the dye multimer and the sodium ion and the potassium ion in the composition is inhibited, , Compatibility of other components (for example, resin, monomer, solvent, etc.) in the composition can be improved. This makes it possible to more effectively suppress the phase separation of the pigment structure and other components in the composition. As a result, in the case of forming the composition for a long period of time under a low-temperature environment (for example, a refrigerated storage state), the generation of foreign matter can be suppressed more effectively.

In addition, when at least one of the sodium ion concentration and the potassium ion concentration is 0.1 ppm or more, the compatibility of the pigment structure and other components can be prevented from becoming too high, and consequently, the generation of foreign matter can be suppressed more effectively have.

Particularly, the sodium ion concentration and the potassium ion concentration in the composition are preferably 1 to 10 ppm, more preferably 3 to 7 ppm. By adjusting to such a range, the effect of the present invention can be achieved more effectively.

In the composition of the present invention, the concentration of toluene in the composition is preferably 1 to 13 ppm, more preferably 2 to 10 ppm, and even more preferably 3 to 7 ppm. By adjusting the toluene concentration to such a range, when the coloring pattern formed using the composition of the present invention is left behind for a long time, the line width of the pattern can be more effectively uniformed. The term "long-term retardation" refers to leaving the film for a long time after forming the film using the composition and forming i-line exposure at the time of forming the colored pattern.

By setting the toluene concentration to 13 ppm or less, it is possible to effectively inhibit toluene from aggregating unnecessary components (such as a curable compound) in the composition more than necessary. As a result, phase separation does not occur even if the delay is left for a long time, and the line width of the pattern can be kept more uniform.

When the concentration of toluene is 1 ppm or more, compatibility of the cationic moiety in the dye structure with the minority components in the composition can be improved, and even if the retardation is left for a long time, phase separation does not occur and the line width of the pattern becomes more uniform . For example, the line width of the pattern can be more uniformly maintained even when the delay time is set to 2 days or more, the pattern size is set to 1.0 mu m, and 1.0 wt% of tetramethylammonium hydroxide is used as the developer after exposure.

The composition of the present invention preferably has a water content in the composition of 0.1 to 5% by mass, more preferably 0.1 to 1% by mass, and further preferably 0.2 to 0.5% by mass.

By controlling the water content to 3 mass% or less, it is possible to more effectively suppress the separation of the cation portion and the anion portion in the dye multimer. In the film formed in a state in which the cation site and the anion site are difficult to separate, the photoexcited dye radical is hardly trapped (trapped) by oxygen under a low oxygen concentration, and the dye is more difficult to decompose.

When the water content is 0.1 mass% or more, the distance between the cation site and the anion site is not so close to each other, so that the energy transfer and electron transfer at the time of photoexcitation are hardly caused, so that the dye is less likely to decompose. As a result, it is possible to maintain a good light resistance even if it is left for a long time under a low oxygen concentration.

In particular, good light resistance can be maintained even when irradiated for two months or more at an illuminance of 500 lux under a low oxygen concentration.

The composition of the present invention preferably has a solid-state voltage holding ratio of 10 to 80%, more preferably 60 to 99%, and even more preferably 80 to 99%, from the viewpoint of long-term thermal cycle performance.

Further, in the present invention, by using the above-described constitution, a coloring composition having a small rate of change in viscosity after a long period of time can be obtained. For example, at room temperature (23 DEG C) for at least three months, the rate of change in viscosity can be reduced. Further, in the present invention, a coloring composition having a low rate of occurrence of foreign matter can be obtained when it is placed for a long time under various environments (for example, -30 to 150 DEG C) and / or high humidity (for example, relative humidity of 80% . For example, the occurrence rate of the foreign matter can be reduced even when it is left for one month or more under the environment of freezing (-15 ° C or less), or for two weeks or more under the environment of 110 ° C and 85% RH.

The composition of the present invention is preferably used for forming a colored layer of a color filter. The coloring composition of the present invention preferably includes a curable compound and a pigment. As the curable compound, a polymerizable compound or an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group) is exemplified and appropriately selected according to the application and the production method. Further, the coloring composition of the present invention preferably contains a photopolymerization initiator.

For example, in the case of forming a colored layer by photoresist, it is preferable that the colored composition of the present invention contains a colorant, a pigment, a solvent, an alkali-soluble resin as a curable compound, a pigment, and a photopolymerization initiator. In addition, it may contain a component such as a surfactant.

Further, in the case of forming a colored layer by dry etching, it is preferable to include a dye multimer, a solvent, a polymerizable compound as a curable compound, a pigment, and a photopolymerization initiator. In addition, it may contain a component such as a surfactant.

<< (A) Coloring matter >>

The dye multimer includes a structure such as a dimer, a trimer and a polymer. The colorant oligomer functions as, for example, a coloring agent in the coloring composition of the present invention.

The maximum absorption wavelength of the dye multimer is preferably 420 to 700 nm, more preferably 450 to 650 nm.

The acid value of the colorant oligomer is preferably 5 to 100 mgKOH / g, and more preferably 15 to 60 mgKOH / g.

In the present invention, the repeating unit having a structure derived from a coloring matter is preferably from 10 to 100 mol%, more preferably from 50 to 100 mol%, based on 100 mol% of the total repeating units, , And particularly preferably from 60 to 100 mol%.

The dye multimer has a partial structure and an anion site derived from a xanthine dye having a cation moiety. Preferable examples of the dye multimer include the following.

(A1) A dye multimer comprising a repeating unit having a partial structure derived from a xanthine dye having a cation moiety and having a counter anion moiety.

(A2) a dye unit having a repeating unit having a partial structure derived from a xanthine dye having a cation moiety, wherein the dye structure has an anionic moiety.

(A3) A dye multimer comprising a monomer having a partial structure derived from a xanthine dye having a cation moiety and a repeating unit having a counter anion moiety.

(A4) In the above, a pigment multimer having further other cation and anion sites.

Hereinafter, each mode will be described in detail.

<<< (A1) >>>

<<<< Against negative ions >>>>

The counter anion moiety of the dye-sensitized compound (A) is preferably an acetonuclear moiety. Non-nucleophilic means a property of not attacking pigments with nuclei by heating.

The counter anion may be an organic anion, an inorganic anion, or an organic anion. As an example of negative ions, those described in Japanese Patent Application Laid-Open No. 2007-310315, paragraph number 0075, which are incorporated herein by reference.

Preferably, the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion, tetra aryl borate anions, 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 is 1 to 4) and PF _n2 R ^P _(6-n2) ^- (wherein R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms and n2 is an integer of 1 to 6 , And more preferably selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion and a tetraaryl borate anion, more preferably a bis (sulfonyl) imide anion Do. By using such a counter anion, the effect of the present invention tends to be more effectively exerted.

As the bis (sulfonyl) imide anion, a structure represented by the following general formula (AN-1) is preferable.

[Chemical Formula 1]

(In the formula (AN-1), X ¹ and X ² each independently represent an alkyl group having 1 to 10 carbon atoms having a fluorine atom or a fluorine atom, and X ¹ and X ² may be bonded to each other to form a ring .)

X ¹ and X ² each independently represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom or a fluorine atom and is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom or a fluorine atom, More preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and still more preferably a trifluoromethyl group.

The tris (sulfonyl) methide anion is preferably a structure represented by the following general formula (AN-2).

(2)

(In the formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or an alkyl group having a fluorine atom of 1 to 10 carbon atoms.)

X ³ , X ⁴ and X ⁵ are, independently of each other, the same as X ¹ and X ² , and the preferred ranges are also the same.

The tetraarylborate anion is preferably a compound represented by the following formula (AN-5).

(3)

(In the formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group.)

Each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is 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.

The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have 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 sulfonamido group and a nitro group, More preferably a fluorine atom or an alkyl group, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a phenyl group having an alkyl group having a halogen atom and / or a halogen atom, more preferably a phenyl group having an alkyl group having a fluorine atom and / More preferable.

The counter anion moiety is ^a group represented by -B (CN) _n1 (OR ^a ) ₄ _-n 1 (wherein R ^a represents an alkyl group having from 1 to 10 carbon atoms or an aryl group having from 6 to 10 carbon atoms and n 1 represents an integer of from 1 to 4) . R ^a as an alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R ^a as an 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 or 2.

The counter anion moiety is also preferably -PF ₆ R ^P _{(6-n 2)} ^- (wherein R ^P is a fluorinated alkyl group having 1 to 10 carbon atoms and n 2 is an integer of 1 to 6). R ^P is preferably an alkyl group having 1 to 6 carbon atoms and more preferably a fluorine atom having 1 to 4 carbon atoms, 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 opposite anion site is preferably 100 to 1,000, more preferably 200 to 500.

The dye multimer may contain only one kind of opposite anion moiety, or two or more kinds thereof.

Specific examples of counter anion sites are shown below, but the present invention is not limited thereto.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

<<<< Pigment structure >>>>

The dye structure in the present invention is a partial structure derived from a xanthine dye having a cation moiety and is a dye moiety in which a hydrogen atom is removed from a specific dye capable of forming a dye structure (hereinafter also referred to as a dye compound) A polymer chain or a core of a dendrimer). The details of these will be described below.

The dye structure is not particularly limited as long as it has a structure derived from a xanthate dye having a cation moiety, and various structures including known ones can be applied.

The pigment-form oligomer (A) includes a partial structure derived from a chiffon compound represented by the following general formula (J) as a partial structure of a pigment moiety.

[Chemical Formula 8]

(In the formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁸⁵ independently represents a monovalent substituent, Represents an integer of 0 to 5. X ^- represents an opposite anion moiety.)

The substituent groups R ⁸¹ to R ⁸⁴ and R ⁸⁵ in the general formula (J) can take are the same as the substituents exemplified in Substituent Group A described later.

R ⁸¹ and R ⁸² in the general formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to form a 5-membered, 6-membered or 7-membered ring or 5 A 6-membered or 7-membered unsaturated ring. When the 5-membered, 6-membered or 7-membered ring formed is a further substitutable group, the substituent may be substituted with a substituent described for R ⁸¹ to R ^85, and when the substituent is substituted with two or more substituents, They may be the same or different.

R ⁸¹ and R ⁸² in the general formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to form a 5-membered, 6-membered or 7-membered When the unsaturated ring is a 5-membered, 6-membered or 7-membered unsaturated ring, the 5-membered, 6-membered or 7-membered unsaturated ring having no substituent or the 5-membered, A thiazole ring, an imidazole ring, a thiazole ring, an oxazole ring, a thiazole ring, a pyrrole ring, a piperidine ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, a pyridine ring A furan ring, a pyrazine ring, and a pyridazin ring, preferably a benzene ring and a pyridine ring.

In particular, it is preferable that R ⁸² and R ⁸³ are a hydrogen atom or a substituted or unsubstituted alkyl group, and R ⁸¹ and R ⁸⁴ are a substituted or unsubstituted alkyl group or a phenyl group. R ⁸⁵ is preferably a halogen atom, a straight or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamido group, a carboxyl group, or an amido group, and more preferably a sulfo group, a sulfonamido group, a carboxyl group, desirable. It is preferred that R ⁸⁵ is bonded to the adjacent portion of the carbon linked to the residual ring. The substituent of the phenyl group of R ⁸¹ and R ⁸⁴ is particularly preferably a hydrogen atom, a halogen atom, a straight-chain or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamido group or a carboxyl group.

The compound having a xanthane skeleton represented by the general formula (J) can be synthesized by a method described in the literature. Specifically, Tetrahedron Letters, 2003, vol. 44, No. 23, pp. 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pp. 3097-3106, and the like can be applied.

Specific examples of the xanthene compound are shown below, but the present invention is not limited thereto.

[Table 1]

[Table 2]

[Chemical Formula 9]

[Chemical formula 10]

The hydrogen atom in the dye structure may be substituted by a substituent selected from Substituent Group A below unless the purpose of the present invention is deviated from the dye multimer.

Substituent group A:

Examples of the substituent which the dye multimer may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, An alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group (including an alkylamino group and an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, An alkylsulfonylamino group, an alkylsulfonylamino group, an alkylsulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, an arylsulfinyl group, , An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or a heterocyclic azo group, an imido group, a phosphino group, a phosphinoyl group, Sulfinyl there may be mentioned an amino group, a silyl group or the like. This will be described in detail below.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms (Preferably 3 carbon atoms) such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2- chloroethyl, 2-cyanoethyl, A substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms such as cyclohexyl and cyclopentyl, and a polycycloalkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted C 5 -C 30 alkyl group A bicycloalkyl group such as bicyclo [1,2,2] hept-2-yl, bicyclo [2,2,2] octen-3-yl), or a tricycloalkyl group More preferably a monocyclic cycloalkyl group, a bicyclic cycloalkyl group, An alkyl group as a cycle, a monocyclic cycloalkyl group is particularly preferred),

A straight chain or branched alkenyl group (linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl) (Preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl) (Preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, such as bicyclo [2,2,1] hept-2-yl), a cycloalkenyl group such as a bicycloalkenyl group 1-yl, bicyclo [2,2,2] oct-2-en-4-yl) or tricycloalkenyl group and monocyclic cycloalkenyl group is particularly preferable), an alkynyl group , A substituted or unsubstituted alkanyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilyl The group),

(Preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecylhexylaminophenyl), a heterocyclic group Is preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or polycyclic heterocyclic group, more preferably the ring constituent atom is selected from a carbon atom, a nitrogen atom and a sulfur atom, A heterocyclic group having at least one hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. , 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl and 2-benzothiazolyl), a cyano group, a hydroxyl group, a nitro group,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxy (Preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy , 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethyl (Preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, and the hetero ring moiety is a hetero ring moiety having a hetero ring moiety described by the above-mentioned heterocyclic group), a heterocyclic oxy group For example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, (Preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, and examples of the substituted or unsubstituted carbamoyloxy group include a substituted or unsubstituted carbamoyloxy group, a substituted or unsubstituted carbamoyloxy group, a substituted or unsubstituted carbamoyloxy group, For example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, Alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n - octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryl group having 7 to 30 carbon atoms Brassica is the carbonyloxy group, e.g., phenoxy-carbonyl-oxy, p- methoxyphenoxy-oxy-carbonyl, p-n- hexadecyl oxy-phenoxy-carbonyl-oxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms, (Preferably a formylamino group having 1 to 5 carbon atoms, such as methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin- A substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms and includes, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoyl Amino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms such as carbamoyl Amino, N, N-dimethylaminocarbonylamino, N, N- Aminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxy Carbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxy Phenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn (Preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, and examples thereof include a substituted or unsubstituted arylsulfonylamino group, For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group,

Alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a carbon number A substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 to 30 And the heterocyclic moiety is preferably a heterocyclic moiety as described above for the heterocyclic group, and examples thereof include 2-benzothiazolylthio, 1-phenyltetrazol-5-yl A sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N , N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl)

Alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, (Preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a methylsulfonyl group, an isopropylsulfonyl group, (Preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 2 to 30 carbon atoms, A substituted or unsubstituted arylcarbonyl group such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group A substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o -Chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl ), A carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, (preferably a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 3 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 3 to 30 carbon atoms, The heterocyclic azo group (the heterocyclic moiety is preferably a heterocyclic moiety described above for the heterocyclic group), for example, phenylazo, p-chlorophenyl azo, 5-ethylthio-1,3,4-thiadiazole 2-yl azo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as N-succinimide, N-phthal A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphine group (for example, Preferably a substituted or unsubstituted phosphinil group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

(Preferably a substituted or unsubstituted phosphinioxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferable Is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, and includes, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted aryl group having 3 to 30 carbon atoms Or an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

Of the above functional groups, those having a hydrogen atom may be those in which the hydrogen atom in the functional group is substituted with any of the above-mentioned groups. Examples of the functional group that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group, and specific examples include methylsulfonylaminocarbonyl , p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

&Lt; Structure of pigment multimers &

The colorant oligomer (A) to be used in the coloring composition of the present invention is not particularly defined, but may be a colorant oligomer having at least one of the repeating units represented by the following general formulas (a1-1) and (a1-2) Or a large amount of a dye represented by the general formula (a1-3). The repeating unit represented by the general formula (a1-1) may be contained in only one kind or two or more kinds of repeating units in one kind of pigment oligomer. In addition, as described later, other repeating units may be contained.

In the present invention, it is preferable to include a dye multimer represented by the general formula (a1-1). These are explained in order.

<< Repeating unit represented by the general formula (a1-1) >>

In general formula (a1-1)

(11)

(In formula (a1-1), X ¹ represents a group forming a main chain, L ¹ represents a single bond or a divalent linking group, and Dye I represents a dye structure having a cationic site.)

Hereinafter, general formula (a1-1) will be described in detail.

In the general formula (a1-1), X ¹ represents a group forming a main chain. That is, a part forming a repeating unit corresponding to a main chain formed by a polymerization reaction. X ¹ is preferably a linking group represented by any one of the following formulas (XX-1) to (XX-24), more preferably a linking group represented by any one of formulas (XX-1) More preferably selected from a (meth) acrylic linkage chain represented by (XX-10) to (XX-17) and a vinyl-based linkage chain represented by (XX-24) (Meth) acrylic linkage chain represented by the formula (1) and (XX-2) and the styrene-based linkage chain represented by the formula (XX-11).

(XX-1) to (XX-24), it is connected to L ¹ at the site indicated by *.

Me represents a methyl group. In the formulas (XX-18) and (XX-19), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

[Chemical Formula 12]

In formula (a1-1), L ¹ represents a single bond or a divalent linking group. When L ¹ represents a divalent linking group, examples of the divalent linking group include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc.) , A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group or a naphthalene group), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, C (= O) -, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and a linking group formed by connecting two or more thereof. L ¹ is a single bond or an alkylene group, more preferably a single bond or - (CH ₂ ) n- (n is an integer of 1 to 5). Here, R represents, independently of each other, a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The divalent linking group represented by L < ^{1 >} may be an ionic or coordinate bond with DyeI. In this case, either an anionic group or a cationic group may be used.

As the anionic ^{_{^{group, -COO -, -PO 3 H -}}} , -SO 3 -, -SO 3 NH -, -SO 3 N - there may be mentioned, such as ^{_{^{CO-, -COO -, -PO 3 H -}}} , -SO ₃ ^- is preferred.

Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium, and phosphonium), and particularly preferable are ammonium cations.

When the L ¹ having an available DyeI and ionic bond, or coordinate bond, L ¹ is the anion portion that has a DyeI ^{_{^{(-COO -, -SO 3 -,}}} -O - , etc.) or a cationic unit (the onium cation or a metal cation Etc.).

In the general formula (a1-1), DyeI represents a dye structure derived from the above-mentioned dye compound.

The pigment oligomer having a repeating unit represented by the general formula (a1-1) is obtained by (1) a method of synthesizing a monomer having a pigment residue by addition polymerization, (2) a method of synthesizing a monomer having a pigment residue by an isocyanate group, an acid anhydride group, (A hydroxyl group, a primary or secondary amino group, a carboxyl group, or the like) capable of reacting with a highly reactive group.

Addition polymerization known in the art (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, and among these, the synthesis by radical polymerization in particular makes it possible to mild the reaction conditions and does not decompose the pigment structure Do. For the radical polymerization, known reaction conditions can be applied.

Among them, the dye oligomer having a repeating unit represented by the general formula (a1-1) is preferably a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance.

Specific examples of the repeating unit represented by formula (a1-1) are shown below, but the present invention is not limited thereto.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

<< Repeating unit represented by the general formula (a1-2) >>

Next, details of the dye multimer represented by the general formula (a1-2) will be described.

In general formula (a1-2)

[Chemical Formula 16]

(In formula (a1-2), L ³ represents a single bond or a divalent linking group, DyeIII represents a dye structure having a cationic site, and m represents 0 or 1.)

In the general formula (a1-2), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ³ include a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group or a naphthalene group), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, (R represents each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C (= O) -, -SO-, -SO ₂ -, and a linking group formed by connecting two or more thereof .

m represents 0 or 1, but is preferably 1.

Specific examples of suitable divalent linking groups represented by L ³ in general formula (a1-2) are described below, but L ³ of the present invention is not limited thereto. In addition, a region indicated by * indicates a connection site with DyeIII and the like.

[Chemical Formula 17]

[Chemical Formula 18]

The dye multimer having the repeating unit represented by the general formula (a1-2) is synthesized by the sequential polymerization. The term " sequential polymerization " means that the polymerization is carried out in the presence of a polymerization initiator (for example, a reaction between a diisocyanate compound and a diol, a reaction between a diepoxy compound and a dicarboxylic acid, a reaction between a tetracarboxylic acid dianhydride and a diol, , Reaction of dicarboxylic acid with diol, reaction of dicarboxylic acid with diamine, etc.). Among them, it is preferable to synthesize the intermediate part by the reaction, because the reaction condition can be tempered and the pigment structure is not decomposed. For the cyclic polymerization, known reaction conditions can be applied.

Specific examples of the repeating unit represented by formula (a1-2) are shown below, but the present invention is not limited thereto.

[Chemical Formula 19]

&Lt; < Colorant substance represented by formula (a1-3) >

Next, the dye multimer represented by the general formula (a1-3) will be described in detail.

In general formula (a1-3)

[Chemical Formula 20]

(In the general formula (a1-3), L ⁴ represents an n-valent linking group, and n represents an integer of 2 to 20. Dye IV represents a pigment structure having a cation site.)

In the general formula (a1-3), n is preferably 3 to 15, and particularly preferably 3 to 6.

In the general formula (a1-3), when n is 2, the divalent linking group represented by L ⁴ includes a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -NR- (R is each independently a hydrogen atom, an alkyl group, an aryl group, or heterocyclic group), -C (= O) - , -SO-, -SO 2 - , And a linking group formed by connecting two or more of them.

The n-valent linking group wherein n is 3 or more is a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8-naphthalene group, etc.) A linking group (for example, a 1,3,5-triazine group or the like), an alkylene linking group or the like as a central nucleus and substituted by the above-mentioned bivalent linking group.

Specific examples of L ⁴ in general formula (a1-3) are shown below, but the present invention is not limited thereto. In addition, a portion indicated by * indicates a connection site with DyeIV.

[Chemical Formula 21]

Specific examples of Dye IV in general formula (a1-3) are shown below, but the present invention is not limited thereto.

[Chemical Formula 22]

(A1-1) and (a1-2), among the dye oligomers having at least one repeating unit represented by the general formula (a1-1) and the repeating unit represented by the general formula (a1-2) (A1-2), and a pigment oligomer having a repeating unit represented by the general formula (a1-2) and a colorant multimer represented by the general formula (a1-3) Is covalently bonded to the molecular structure, the coloring composition containing the dye multimer is excellent in heat resistance. Therefore, it is preferable that the coloring composition is applied to the pattern formation with a high-temperature process, because it is effective in inhibiting the dye transfer to other adjacent coloring patterns. In particular, the compound represented by the general formula (a1-1) is preferable because it is easy to control the molecular weight of the dye multimer.

<< Other functional groups and repeating units >>

The dye multimer may have another functional group in the dye structure portion of the above-mentioned dye multimer. Examples of other functional groups include a polymerizable group, an acid group, and an alkali-soluble group.

The dye multimer may contain other repeating units in addition to the repeating units containing the above-described dye structures. The other repeating unit may have a functional group.

Examples of other repeating units include repeating units containing at least one of a polymerizable group, an acid group, and an alkali-soluble group.

That is, the dye multimer may have other repeating units in addition to the repeating units represented by the general formulas (a1-1) to (a1-3). The other repeating units may be contained in only one kind or two or more kinds in one coloring matter multimer.

Further, the dye multimer may have other functional groups in the dye multimer represented by the general formulas (a1-1) to (a1-3). The details of these will be described below.

<<< Polymerizable group of the colorant multimer (A) >>>

It is preferable that the dye multimer contains a polymerizable group. The polymerizable group may be contained only in one kind or in two or more kinds.

The polymerizable group may contain a polymerizable group in the dye structure, or may contain another portion. In the present invention, it is preferable that the dye structure includes a polymerizable group. With such a constitution, the heat resistance tends to be improved.

Further, in the present invention, an aspect in which a portion other than the dye structure includes a polymerizable group is also preferable.

As the polymerizable group, known polymerizable groups that can be crosslinked by radicals, acids, and heat can be used, and examples thereof include groups containing an ethylenic unsaturated bond, cyclic ethers (epoxy groups, oxetane groups) Particularly a group containing an ethylenically unsaturated bond is preferable, and a (meth) acryloyl group is more preferable, and a glycidyl group derived from glycidyl (meth) acrylate and 3,4-epoxy-cyclohexylmethyl (meth) (Meth) acryloyl group is more preferable.

The polymerizable group is preferably contained as a repeating unit having a polymerizable group in the polymeric oligomer, more preferably as a repeating unit having an ethylenically unsaturated bond. In other words, an example of a preferred embodiment of the dye multimer is that the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having a polymerizable group, wherein the repeating unit containing a dye monomer and the dye having an ethylenically unsaturated bond And more preferably contains a repeating unit.

As a method of introducing the polymerizable group, there are (1) a method of modifying a dye multimer with a polymerizable group-containing compound, and (2) a method of copolymerizing the dye monomer and a polymerizable group-containing compound. This will be described in detail below.

(1) Method of modifying a dye multimer with a polymerizable group-containing compound and introducing it:

As a method for modifying a dye multimer with a polymerizable group-containing compound and introducing it, a known method can be used without particular limitation. (B) a method in which a hydroxyl group or an amino group having a dye oligomer is reacted with an unsaturated bond-containing isocyanate compound; (c) a method of reacting a carboxylic acid having an unsaturated bond- c) a method of reacting an epoxy compound possessed by a dye multimer with an unsaturated bond-containing carboxylic acid compound is preferable from the standpoint of production.

Examples of the unsaturated bond-containing epoxy compound in the method of reacting the carboxylic acid having a dye oligomer with the unsaturated bond-containing epoxy compound (a) include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3,4 Epoxy-cyclohexylmethyl acrylate, and 3,4-epoxy-cyclohexylmethyl methacrylate. Particularly, glycidyl methacrylate and 3,4-epoxy-cyclohexylmethyl methacrylate are cross- And is excellent in stability and storage stability. As the reaction conditions, known conditions can be used.

isocyanatoethyl methacrylate, 2-isocyanatoethyl methacrylate, and 2-isocyanatoethyl methacrylate in the method (b) of reacting the hydroxyl group or the amino group of the dye oligomer with the unsaturated bond-containing isocyanate compound -Isocyanatoethyl acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Of these, 2-isocyanatoethyl methacrylate has a crosslinking property and storage stability Which is preferable. As the reaction conditions, known conditions can be used.

(c) a carboxylic acid compound having a known (meth) acryloyloxy group as the unsaturated bond-containing carboxylic acid compound in the method of reacting an epoxy compound possessed by a dye oligomer with an unsaturated bond-containing carboxylic acid compound can be used without particular limitation, Methacrylic acid and acrylic acid are preferable, and methacrylic acid is particularly preferable since it is excellent in crosslinking property and storage stability. As the reaction conditions, known conditions can be used.

(2) Method of copolymerizing and introducing the dye monomer and the polymerizable group-containing compound:

(2) A method of copolymerizing and introducing the dye monomer and the polymerizable group-containing compound is not particularly limited, and known methods can be used. (D) a method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable group containing a polymerizable group, (e) a method of copolymerizing a middle part-capable dye monomer and a middle part capable polymerizable group-containing compound is preferable.

(d) an allyl group-containing compound (for example, allyl (meth) acrylate, etc.) as a radically polymerizable group containing a polymerizable compound in a method of copolymerizing a radically polymerizable dye monomer with a radically polymerizable polymerizable group- Epoxy group-containing compounds (e.g., (meth) acrylate glycidyl, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, (Meth) acrylate), methylol group-containing compounds (e.g., N- (hydroxymethyl) acrylamide and the like), and epoxy compounds and oxetane compounds are particularly preferable. As the reaction conditions, known conditions can be used.

(e) a polymerizable group-containing intermediate compound capable of being polymerized in a method of copolymerizing a middle part-capable colorant monomer with a middle-partable polymerizable group-containing compound, wherein the unsaturated bond-containing diol compound (for example, 2,3-dihydroxy Propyl (meth) acrylate, etc.). As the reaction conditions, known conditions can be used.

As a method of introducing a polymerizable group, a method of reacting a carboxylic acid having a dye multimer with an unsaturated bond-containing epoxy compound is particularly preferable.

The amount of the polymerizable group possessed by the dye oligomer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and particularly preferably 0.3 to 1.0 mmol based on 1 g of the colorant oligomer (A).

The proportion of the repeating unit containing a polymerizable group as the pigment multimer is preferably, for example, 5 to 50 moles, more preferably 10 to 20 moles, per 100 moles of the total repeating units.

Examples of the repeating unit having a polymerizable group include the following specific examples. However, the present invention is not limited thereto.

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&Lt; EMI ID =

Among the above embodiments, from the viewpoint of substrate adhesion and surface roughness, a dye monomer having an ethylenically unsaturated bond is preferable, and among these, a methacryloyl group, an acryloyl group, a styryl group, or a vinyloxy group is preferable, More preferably a methacryloyl group, and more preferably a methacryloyl group.

<<< Acid and alkali-soluble groups of the dye (A) >>>

Examples of the acid group which the dye multimer may have include a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. Examples of the alkali-soluble group include a phenolic hydroxyl group and a carboxylic acid group.

In the present invention, the acid group and / or alkali-soluble group is preferably a repeating unit having an acid group and / or an alkali-soluble group and contained in the colorant oligomer.

The acid value of the repeating unit having an acid group is preferably from 15 mgKOH / g to 110 mgKOH / g, more preferably from 20 mgKOH / g to 90 mgKOH / g, still more preferably from 30 mgKOH / g to 60 mgKOH / g.

The acid value of the dye multimer can be calculated from, for example, the average content of the acid groups in the dye multimer. Further, by changing the content of the monomer unit containing an acid group constituting the dye multimer, a resin having a desired acid value can be obtained.

Examples of a method of introducing an alkali-soluble group into a dye multimer include a method of previously introducing an alkali-soluble group into the dye monomer and a method of dissolving a monomer other than the dye monomer having an alkali-soluble group (such as (meth) acrylic acid, caprolactone modified product of acrylic acid, (Meth) acrylate modified with phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-cyclohexanedicarboxylic anhydride modified product of 2-hydroxyethyl (meth) acrylate, Carboxylic acid-containing monomers such as styrene carboxylic acid, itaconic acid, maleic acid and norbornenecarboxylic acid, phosphoric acid-containing monomers such as acid phosphoxyethyl methacrylate and vinylphosphonic acid, vinyl sulfonic acid, 2-acrylamide- Containing sulfonic acid-containing monomers), but it is more preferable to use both methods.

The amount of the alkali soluble group possessed by the dye oligomer is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and particularly preferably 0.5 mmol to 1.0 mmol, per 1 g of the colorant multimer.

When the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having an acid group, the proportion of the repeating unit containing an acid group-containing repeating unit is preferably in the range of, for example, 100 moles per 100 moles of the repeating unit containing the dye monomer Is preferably 5 to 70 mols, and more preferably 10 to 50 mols.

Examples of other functional groups of the dye oligomer include a development promoter such as lactone, acid anhydride, amide, -COCH ₂ CO- and cyano group, a long chain and cyclic alkyl group, an aralkyl group, an aryl group, a polyalkylene oxide group, , A maleimide group, and an amino group, and the like, and they can be suitably introduced.

As an introduction method, there may be mentioned a method of introducing into the dye monomer in advance, and a method of copolymerizing the monomer having the functional group.

Specific examples of the repeating unit having other functional groups possessed by the dye-polymer multimer are shown, but the present invention is not limited thereto.

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(26)

(27)

(28)

[Chemical Formula 29]

<<< (A2) >>>

The form of the pigment oligomer (A2) is a pigment multimer containing a repeating unit having a pigment structure, and having a pigment structure of an anion site.

For example, the dye multimer preferably contains a repeating unit represented by the general formula (a2).

(A2)

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(In the general formula (a2), X ¹ represents a group forming a main chain, and L ¹ represents a single bond or a divalent linking group.) DyeIA represents a dye structure having a cation site and an anion site.

In the general formula (a2), X ¹ and L ¹ are the same as the general formula (a1-1) described above, and the preferable range is also the same.

In the general formula (a2), DyeIA has DyeI in the above-mentioned general formula (a1-1) further having an anion site. Examples of the anion moiety include -SO ₃ ^- , -CO ₂ ^2- , and the like.

As specific examples of the form of the pigment oligomer (A2), reference can be made to A-1 and A-3 to A-6 described in paragraph 0069 of Japanese Laid-Open Patent Publication No. 2012-032754, the contents of which are incorporated herein by reference.

<<< (A3) >>>

The form of the pigment oligomer (A3) is a pigment multimer containing a monomer having a pigment structure and a repeating unit having a counter anion site.

The monomer having a dye structure is equivalent to a monomer containing a partial structure derived from the xanthine compound represented by the above-mentioned general formula (J).

The repeating unit having a counter anion moiety preferably includes a repeating unit represented by the following formula (a3).

(A3)

(31)

(In the general formula (a3), X ¹ represents a group forming a main chain, L ² represents a single bond or a divalent linking group, and Z represents a structure having a counter anion site.)

In the general formula (a3), X ¹ is the same as the general formula (a1-1) described above, and the preferable range is also the same.

In the general formula (a3), when L ² represents a divalent linking group, an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), an arylene group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) An alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), an arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) An alkylcarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), an arylcarbonyl group having 6 to 20 carbon atoms (preferably 6 to 11 carbon atoms), an alkylamino group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) An arylcarbonyloxy group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), an arylcarbonyloxy group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), an alkylcarbonyloxy group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) And the like. These divalent linking groups are preferably substituted with an electron attractive group, and examples of the electron attractive groups include a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), a nitro group, a cyano group, A halogenated alkyl group (e.g., a trifluoromethyl group), and a halogenated aryl group.

L ² is an alkylene group (fluorinated alkylene group) substituted with a fluorine atom having 1 to 10 carbon atoms when Z in the general formula (a3) described above is a low nucleophilic anion structure represented by the following general formula (2-1) .

In the general formula (a3), Z preferably represents a group represented by the general formula (2-1), a fluorinated alkylsulfonimide group or a fluorinated alkylsulfonimide group, or a group represented by the general formula (2-3).

In general formula (2-1)

-Y ¹ -A ¹

(In the general formula (2-1), * represents a bonding site with L ² in the general formula (a3), Y ¹ represents a fluorinated alkylene group, and A ¹ represents SO ₃ ^- .

(2-3)

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(* In the general formula (2-3) represents a bonding site with L ² in the general formula (a3), and R represents a cyano group or a fluorinated alkyl group, preferably a cyano group.

Specific examples of the repeating unit represented by the general formula (a3) used in the present invention are shown below, but the present invention is not limited thereto. The specific example shows a state in which the anion site is not dissociated, but it goes without saying that the state in which the anion site is dissociated is also within the scope of the present invention.

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<<< (A4) >>>

The form of the pigment multimer (A4) is a pigment multimer having further other cation and anion moieties. For example, it is a pigment multimer having a monomer having a pigment structure and a monomer having a pigment structure and having a repeating unit having a cation moiety, and containing a corresponding anion moiety.

As the repeating unit having a cationic site, reference can be made to the description in paragraphs 0018 to 0061 of Japanese Laid-Open Patent Publication No. 2011-242752, the contents of which are incorporated herein by reference.

C. I. Acid Red 289 is exemplified as a monomer having a pigment structure and containing a corresponding anion moiety.

As a specific example of the pigment oligomer (A4), reference may be made to the description in paragraph 0165 of Japanese Laid-Open Patent Publication No. 2011-242752, the content of which is incorporated herein by reference.

The weight average molecular weight of the pigment multimer is preferably from 2,000 to 20,000, more preferably from 3,000 to 15,000, and particularly preferably from 4,000 to 10,000.

The weight average molecular weight and number average molecular weight can be determined by gel permeation chromatography (GPC).

The ratio [Mw / (Mn)] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the pigment multimer is preferably 1.0 to 3.0, more preferably 1.6 to 2.5, Particularly preferably 2.0 to 2.0.

The glass transition temperature (Tg) of the dye multimer is preferably 50 ° C or higher, more preferably 100 ° C or higher. In addition, the 5% weight reduction temperature by the thermogravimetric analysis (TGA measurement) is preferably 120 ° C or higher, more preferably 150 ° C or higher, and still more preferably 200 ° C or higher.

Further, the extinction coefficient per unit weight of the dye multimer (hereinafter, referred to as? ') Is preferably 30 or more, more preferably 60 or more, More preferably 100 or more. Within this range, it is possible to produce a color filter having good color reproducibility when a color filter is manufactured by applying the coloring composition of the present invention.

The molar extinction coefficient of the dye multimer is preferably as high as possible from the viewpoint of tinting power.

The reduced viscosity of the pigment multimer is preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and still more preferably 6.0 to 7.0, from the viewpoint of dye migration. The reduced viscosity can be measured using, for example, a Ubero type viscometer.

It is preferable that the colorant oligomer is a compound dissolved in the following solvent.

Examples of the solvent include esters (e.g., methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate and methyl 3-methoxypropionate), ethers (e.g., methylcellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.) (For example, toluene, xylene, etc.), and it is preferably dissolved in an amount of 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% By mass or less, more preferably 10% by mass or more and 30% by mass or less. When the coloring composition of the present invention is applied to the production of a color filter or the like in this region, it is possible to reduce the concentration drop due to a suitable application surface shape or elution after coating with other colors.

In the coloring composition of the present invention, the pigment multimer may be used singly or in combination of two or more. When two or more kinds are used, it is preferable that the total amount corresponds to the content to be described later.

The content of the colorant multimer (A) in the coloring composition of the present invention is preferably set after considering the content ratio with the pigment to be described later.

The mass ratio of the pigment to the pigment (pigment / polymer (A) / pigment) is preferably from 0.1 to 5, more preferably from 0.2 to 2, still more preferably from 0.3 to 1.

The coloring composition of the present invention may contain known dyes other than the above-mentioned colorant multimer.

For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301, 6-11614, 2592207, 4808501, US 5667920, US 505950, US 5667920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 Japanese Unexamined Patent Application Publication No. 6-194828, Japanese Unexamined Patent Publication No. 2010-250291, Japanese Unexamined Patent Application Publication No. 2011-95732, Japanese Unexamined Patent Application Publication No. 2012-13945, Japanese Unexamined Patent Application Publication No. 2012-46708, Japanese Unexamined Patent Publication Japanese Patent Application Laid-Open Publication Nos. 2004-46712, 2012-181502, 2012-208494, 2013-28764, and 2013-29760, Are incorporated herein by reference. Examples of the chemical structure include a pyrazole group, a pyromethene group, an anilino group, a triphenylmethane group, an anthraquinone group, a benzylidene group, an oxolane group, a pyrazolotriazole group, a pyridazo group, And pyrrolopyrazole azo methane phosphoric acid, can be used.

<< (B) Solvent >>

The coloring composition of the present invention contains a solvent.

The solvent is not particularly limited so long as it satisfies the solubility of each component and the coating property of the coloring composition, but is preferably selected in consideration of solubility, coating ability, and safety of an ultraviolet absorber, an alkali-soluble resin or a dispersing agent.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, , Methyl lactate, ethyl lactate, alkyloxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Ethoxyacetic acid ethyl, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionate Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) Methyl 2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetra Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ether, diethylene glycol Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Examples of the aromatic hydrocarbon include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, cyclopentanone and the like, and toluene, xylene and the like are suitably used.

Among them, a solvent having a molecular weight in the range of 90 to 135 or a boiling point in the range of 120 to 160 占 폚 is preferable from the standpoint of drying after coating. Examples thereof include acetic acid-n-butyl, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone and cyclopentanone.

It is also preferable to mix two or more kinds of these organic solvents in view of the solubility of the alkali-soluble resin and the shape of the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- Two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate . &Lt; / RTI >

In addition to the above-mentioned viewpoints, these organic solvents contain 10% or more of a solvent having excellent solubility of a dyestuff dye, for example, cyclohexanone, cyclopentanone and propylene glycol monomethylether in a solvent, Can be improved. As a specific example, by containing propylene glycol monomethyl ether acetate as a main agent and containing at least 10% of at least one solvent selected from cyclohexanone, cyclopentanone and propylene glycol monomethyl ether, It is possible to improve the stability of delayed-and-negated operation.

The content of the solvent in the coloring composition is preferably 5 to 90% by mass, more preferably 5 to 60% by mass, and more preferably 10 to 50% by mass, in terms of the total solids concentration of the composition, Is particularly preferable.

The composition of the present invention may contain only one kind of solvent, or two or more types of the solvent. When two or more kinds are included, the total amount is preferably in the above range.

The coloring composition of the present invention preferably contains a curable compound.

As the curable compound, a known polymerizable compound capable of being crosslinked by radicals, acids and heat can be used. For example, a polymerizable compound containing an ethylenic unsaturated bond, cyclic ether (epoxy, oxetane) . The polymerizable compound is suitably selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds from the viewpoint of sensitivity.

Among them, a polyfunctional polymerizable compound is preferable, a polyfunctional polymerizable compound having four or more functionalities is more preferable, a five-or more functional property is more preferable, and a six-functional or more functional property is particularly preferable.

Particularly, a polyfunctional monomer (preferably four or more functionalities, more preferably six or more functional ones) is preferred, and an alkylene oxide-modified one.

Such a group of compounds is well known in the industrial field of the present invention and can be used in the present invention without particular limitation. These may be, for example, monomers, prepolymers, i.e., chemical forms such as dimers, trimer and oligomers or mixtures thereof and their oligomers. The polymerizable compounds in the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like), esters thereof, amides, And esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and oligomers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. Further, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like in place of the above unsaturated carboxylic acid.

As specific compounds of these, the compounds described in paragraphs 0095 to 0108 of JP-A No. 2009-288705 can be suitably used in the present invention.

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 at normal pressure. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and (meth) acrylate, Japanese Examined Patent Publication 48 (Meth) acrylates described in JP-A-41708, JP-A-50-6034, JP-A-51-37193, Polyester acrylates described in JP-B-48-64183, JP-A-49-43191, JP-A-52-30490, epoxies which are reaction products of epoxy resins and (meth) acrylic acid And polyfunctional acrylates and methacrylates such as acrylates, and mixtures thereof.

(Meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether such as glycidyl (meth) acrylate and a compound having an ethylenic unsaturated group.

As other preferable polymerizable compounds, those having a fluorene ring and having an ethylenic unsaturated group as a bifunctional group, such as those described in JP-A-2010-160418, JP-A-2010-129825 and JP-B-4364216, Or more, and a carboxy resin can also be used.

Also, as the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 캜 or higher at normal pressure, the compounds described in paragraphs [0254] to [0257] of JP-A No. 2008-292970 are also suitable.

In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

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(35)

In the above general formula, n is 0 to 14, and m is 1 to 8. R and T present in plural in one molecule may be the same or different.

At least one of the plural Rs present in each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (= O) CH = CH ₂ or -OC ) C (CH ₃₎ represents a group represented by = CH _2.

Specific examples of the polymerizable compounds represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779 Can be used.

Further, in Japanese Patent Application Laid-Open No. 10-62986, ethylene oxide or propylene oxide is added to the above-mentioned polyfunctional alcohol represented by general formulas (1) and (2) together with specific examples thereof and then (meth) acrylated The compound may also be used as a polymerizable compound.

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available products such as KAYARAD D-320; Nippon Kayaku Co., (KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) (Manufactured by Kayaku K.K.), and a structure in which the (meth) acryloyl group intervenes between ethylene glycol and propylene glycol moieties. These oligomer types can also be used.

As the polymerizable compound, a polyfunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, it can be used as it is. If necessary, the hydroxyl group of the above-mentioned ethylenic compound is reacted with a nonaromatic carboxylic acid anhydride, . In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, examples of the monomer having an acid group include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which are obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group . Especially preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd., M-510 and M-520.

These monomers may be used singly or in combination of two or more in view of difficulty in using a single compound in the production process. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer.

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably 5 mg KOH / g to 30 mg KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are deteriorated. If the acid value is too high, the production and handling become difficult, and the photopolymerization performance deteriorates and the curability such as surface smoothness of the pixel becomes poor. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is preferable to adjust the acid groups as the entire polyfunctional monomer to fall within the above range.

It is also preferable that the polymerizable compound contains a polyfunctional monomer having a caprolactone structure.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, Caprolactone obtained by esterifying a polyhydric alcohol such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine and the like with (meth) acrylic acid and epsilon -caprolactone, And lactone-modified polyfunctional (meth) acrylates. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (Z-1) is preferable.

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In the general formula (Z-1), all of the six R's are groups represented by the following formula (Z-2), or one to five of the six R's are groups represented by the following formula (Z-2) Is a group represented by the following general formula (Z-3).

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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.

(38)

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

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (m = 1 in the above formulas (1) (2) = 2, R ¹ are both a hydrogen atom), the group represented by, DPCA-30 (the same formula, m = 1, equation (2) of the group represented by = 3, R ¹ is hydrogen atom DPCA-120 (the same formula, m = 1, the number of groups represented by formula (2) = 6 and R ¹ are all hydrogen atoms), DPCA-120 The number of groups represented by formula (2) = 6, and R ¹ are all hydrogen atoms).

In the present invention, the polyfunctional monomers having a caprolactone structure may be used alone or in combination of two or more.

Also, the specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

[Chemical Formula 39]

E in the general formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) , Y represents independently an integer of 0 to 10, and X represents, independently of each other, an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (Z-4), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is 0 to 40 It is an integer. Provided that when the sum of each m is 0, any one of X is a carboxyl group.

In the general formula (Z-5), the sum of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the total of n is 0 to 60 It is an integer. Provided that when the sum 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. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the general formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum 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.

The - ((CH ₂ ) y CH ₂ O) - or - ((CH ₂ ) y CH (CH ₃ ) O) - in the general formula (Z-4) or the general formula A form in which the terminal is bonded to X is preferable.

The compounds represented by the above general formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the general formula (Z-5), all of the six X's are preferably acryloyl groups.

The total content of the compound represented by the general formula (Z-4) or (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 produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to ring opening skeleton And (meth) acryloyl groups are introduced into the terminal hydroxyl groups of the ring-opening skeleton by reaction with, for example, (meth) acryloyl chloride. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (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 (a) to (f) below (hereinafter also referred to as "exemplified compounds (a) to (f)") , (e) and (f) are preferable.

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Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

As the polymerizable compound, there can be mentioned, for example, those described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293 and JP-A-2-16765 And the ethylene oxide described in JP-A-62-39418, JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, Also suitable are urethane compounds having a skeleton. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 By using the polymerizable compounds, a curable composition having an extremely high photosensitive speed can be obtained.

UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyowa Chemical Industry Co., Ltd.).

JER-827, JER-834, JER-1001, JER-1002, and JER-1003 as the bisphenol A type epoxy resin having an epoxy group as the cyclic ether (epoxy, oxetane) (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.) as the resin, and JER-806, JER-4007, JER-4005, JER- JER-152, JER-157S70, JER-157S65 (above, Japan Epoxy Resin Co., Ltd.) as the phenol novolak type epoxy resin, (EPICLON N-660, EPICLON N-665, EPICLON N-770, and EPICLON N-775 manufactured by DIC Corporation) EPICLON N-670, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (Manufactured by Nippon Kayaku Co., Ltd.), and aliphatic epoxy resins such as ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Side 2083, Celloxide 2085, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of EHPE-3150 (2,2-bis (hydroxymethyl) PB 3600 and PB 4700 (manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L and EX- NC-2000, NC-3000, NC-7300, XD (manufactured by Nippon Shokubai Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP- -1000, EPPN-501, EPPN-502 (manufactured by ADEKA) and JER-1031S (manufactured by Japan Epoxy Resin Co., Ltd.). Such a polymerizable compound is suitable when a pattern is formed by a dry etching method.

The details of the structure of the polymerizable compound, whether or not the polymerizable compound is used alone, whether or not the polymerizable compound is used alone, and the amount thereof to be added can be arbitrarily set in accordance with the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. From the viewpoint of enhancing the strength of the cured film formed by the coloring composition, it is preferable to use a polymer having three or more functional groups and having a different number of functional groups and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene- ) Can be used in combination to control both the sensitivity and the strength. It is more preferable that the polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths is used together in that the developability of the colored composition can be controlled and excellent pattern forming ability can be obtained.

In addition, regarding the compatibility and dispersibility of other components (for example, photopolymerization initiator, dispersant, alkali-soluble resin, etc.) contained in the coloring composition, the method of selecting and using the polymerizable compound is an important factor. For example, The compatibility may be improved by the use of the purity compound or by the combined use of two or more species. In addition, a specific structure may be selected from the viewpoint of improving adhesion with a hard surface such as a support.

The content of the curable compound in the composition of the present invention is preferably 0.1 to 90 mass%, more preferably 1.0 to 60 mass%, and particularly preferably 2.0 to 40 mass%, based on the total solid content in the composition.

The composition of the present invention may contain only one type of curable compound or two or more types of the curable compound. When two or more kinds are included, the total amount is preferably in the above range.

The coloring composition of the present invention preferably further contains (C) a pigment.

As the pigment used in the present invention, various conventionally known inorganic pigments or organic pigments can be used, and it is preferable to use an organic pigment. As the pigment, a high transmittance is preferable.

Specific examples of the inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, And a black pigment such as a composite oxide of the above metal, carbon black, and titanium black.

As the organic pigment, for example,

C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C. I. Pigment Orange 36, 38, 43, 71;

C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C. I. Pigment Violet 19, 23, 32, 39;

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C. I. Pigment Green 7, 36, 37, 58;

C. I. Pigment Brown 25, 28;

C. I. Pigment Black 1;

And the like.

Examples of pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited thereto.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C. I. Pigment Orange 36, 71,

C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C. I. Pigment Violet 19, 23, 32,

C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C. I. Pigment Green 7, 36, 37, 58,

C. I. Pigment Black 1

These organic pigments can be used singly or in various combinations in order to enhance spectral control and color purity. Specific examples of the combination are shown below. As the red pigment, for example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindolin yellow pigment, a quinophthalone pigment A yellow pigment or a mixture with a perylene red pigment can be used. Examples of the anthraquinone pigments include CI Pigment Red 177, and the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224. As the diketopyrrolopyrrole pigments, CI Pigment Red 254, and it is preferable to mix with CI Pigment Yellow 139 in terms of color degradability. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and when the ratio is 100: 51 or more, the dominant wavelength approaches the short wavelength and the color resolution can not be increased. Particularly, the mass ratio is preferably in the range of 100: 10 to 100: 30. Further, in the case of a combination of red pigments, it can be adjusted in accordance with the obtained spectroscopy.

As the green pigment, it is also possible to use a halogenated phthalocyanine pigment alone or in combination with a pigment of a disazo yellow pigment, a quinophthalone yellow pigment, an azomethan yellow pigment or an isophorone yellow pigment Mixing can be used. For example, such examples include CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Mixing with Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine-based pigment may be used singly or a mixture of the phthalocyanine-based pigment and 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 mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

As the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

The coloring composition of the present invention is preferably blended with pigments other than black, and is suitable for blue pigments.

When the pigment is used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness or contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, still more preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.

The primary particle size of the pigment can be measured by a known method such as an electron microscope.

Among them, the pigment is preferably a pigment selected from anthraquinone pigment, diketopyrrolopyrrole pigment, phthalocyanine pigment, quinophthalone pigment, isoindoline pigment, azomethine pigment, and dioxazine pigment . Particularly, CI Pigment Red 177 (anthraquinone pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, 36, 58, CI Pigment Blue 15: 6 ), CI Pigment Yellow 138 (quinophthalone pigment), CI Pigment Yellow 139, 185 (isoindoline pigment), CI Pigment Yellow 150 (azomethine pigment), CI Pigment Violet 23 Is particularly preferable.

In particular, a phthalocyanine pigment is preferable as the pigment.

When a phthalocyanine pigment is used as the pigment, the mass ratio of the phthalocyanine pigment to the above-described pigment oligomer is preferably from 90:10 to 30:70, and more preferably from 65:35 to 55:45.

The content of the pigment is preferably from 10 to 70% by mass, more preferably from 20 to 60% by mass, and still more preferably from 25 to 50% by mass, with respect to the total components excluding the solvent contained in the coloring composition.

When the phthalocyanine pigment is used as the pigment, the content thereof is preferably 25 to 60 mass%, more preferably 30 to 50 mass%, with respect to the total components excluding the solvent contained in the coloring composition, Is 35 to 45% by mass.

The composition of the present invention may contain only one pigment or two or more kinds of pigments. When two or more kinds are included, the total amount is preferably in the above range.

The coloring composition of the present invention preferably contains a photopolymerization initiator from the viewpoint of further improving the sensitivity.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the above-mentioned polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. In addition, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of the monomer.

The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a 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 oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, An oxime compound such as an imidazole or an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoximeether, an aminoacetophenone compound, or a hydroxyacetophenone.

From the viewpoint of exposure sensitivity, it is also possible to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3 -Aryl-substituted coumarin compound is preferable.

More preferably, a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, a triarylimidazole compound, a benzimidazole compound , An onium compound, a benzophenone compound, and an acetophenone compound, and is a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, And at least one compound selected from the group consisting of a thiol compound and a thiol compound is particularly preferable. Further, the triarylimidazole compound may be a mixture with benzimidazole.

Specifically, as the trihalomethyltriazine compound, the following compounds are exemplified. Ph is a phenyl group.

(42)

As the triarylimidazole compound and the benzimidazole compound, the following compounds are exemplified.

(43)

As the trihalomethyltriazine compound, a commercially available product may be used, and for example, TAZ-107 (Midori Kagaku) may be used.

Particularly, when the coloring composition of the present invention is used in the production of a color filter provided in a solid-state image pickup device, it is necessary to form a fine pattern in a sharp shape, and therefore it is important that the coloring composition is developed with no caking Do. From this viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, stepper exposure is used for curing exposure. Since this exposure device is sometimes damaged by halogen and the addition amount of the polymerization initiator needs to be suppressed to a low level, Taking this into consideration, it is particularly preferable to use an oxime compound as the photopolymerization initiator (D) in order to form a fine pattern such as a solid-state image sensor.

As the halogenated hydrocarbon compound having a triazine skeleton, for example, see Wakabayashi et al., Bull. Chem. Soc. Japanese Patent Publication No. 53-133428, the compound described in German Patent Publication No. 3337024, the compound described in JP-A-3337024 by FC Schaefer et al. Org. Chem .; 29, 1527 (1964), compounds described in Japanese Laid-Open Patent Publication No. 62-58241, compounds described in Japanese Laid-Open Patent Publication No. 5-281728, compounds described in Japanese Laid-Open Patent Publication No. 5-34920, A compound described in Japanese Patent Publication No. 4212976, particularly a compound described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph No. 0075, and the like.

As other photopolymerization initiators other than the above, acridine derivatives are exemplified. Specific examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph number 0076, and the contents thereof are incorporated herein by reference.

Examples of the ketone compound include compounds described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph number 0077, and the contents thereof are incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969 or the acylphosphine oxide-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used. As the acylphosphine-based initiator, commercially available products IRGACURE-819 and DAROCUR-TPO (all trade names, manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound. As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of the oxime compounds such as oxime derivatives suitably used as the photopolymerization initiator in the present invention include 3-benzoyloxyiminobutain-2-one, 3-acetoxyiminobutain-2- 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane 1-one, 3- (4-toluenesulfonyloxy) iminobutain-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

Examples of the oxime compounds include JCS Perkin II (1979) pp.1653-1660, JCS Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, The compounds described in the respective publications of JP-A No. 2000-66385, JP-A 2000-80068, JP-A 2004-534797 and JP-A 2006-342166.

IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are suitably used in commercial products.

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Unexamined Patent Publication No. 2009-519904 in which oxime is linked to carbazole N, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in Japanese Unexamined Patent Application Publication Nos. 2002-15025 and 2009-292039 where nitro groups are introduced, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton in the same molecule The compound described in U.S. Patent Publication No. 7556910, the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, or the like may be used.

Preferably, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can be suitably used. Of the cyclic oxime compounds, cyclic oxime compounds that are condensed with a carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 are particularly preferable from the viewpoint of high light-absorbing property and high sensitivity.

The compounds described in JP-A-2009-242469 having an unsaturated bond in a specific part of the oxime compound can also be suitably used because high sensitivity can be achieved by regenerating active radicals from polymerization inert radicals.

Particularly preferred are oxime compounds having a specific substituent group as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

Specifically, as the oxime compound which is a photopolymerization initiator, a compound represented by the following general formula (OX-1) is preferable. Further, 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 form (E) and the form (Z).

(44)

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 an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The above-mentioned substituent may be substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, reference may be made to paragraph 0025 of Japanese Laid-Open Patent Publication No. 2009-191061, which disclosure is incorporated herein by reference.

As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and specifically, reference can be made to paragraph 0026 of Japanese Laid-Open Patent Publication No. 2009-191061, which disclosure is incorporated herein by reference.

As the acyl group, an acyl group having 2 to 20 carbon atoms is preferable. Specifically, reference may be made to paragraph 0033 of Japanese Laid-Open Patent Publication No. 2009-191061, which is incorporated herein by reference.

As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable. Specifically, reference may be made to paragraph 0034 of Japanese Laid-Open Patent Publication No. 2009-191061, which disclosure is incorporated herein by reference.

As the aryloxycarbonyl group, specifically, an aryloxycarbonyl group having 6 to 30 carbon atoms is preferable, and it is possible to refer to Japanese Patent Laid-open Publication No. 2009-191061, paragraph 0035, which is incorporated herein by reference.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specifically, reference can be made to paragraph 0037 of Japanese Laid-Open Patent Publication No. 2009-191061, which disclosure is incorporated herein by reference.

As the alkylthiocarbonyl group, specifically, an alkylthiocarbonyl group having 1 to 20 carbon atoms is preferable, and it is possible to refer to Japanese Patent Laid-Open Publication No. 2009-191061, paragraph 0038, which is incorporated herein by reference.

As the arylthiocarbonyl group, specifically, an arylthiocarbonyl group having 6 to 30 carbon atoms is preferable, and reference can be made to paragraph 0039 of Japanese Laid-Open Patent Publication No. 2009-191061, which disclosure is incorporated herein by reference.

In the general formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The above-mentioned substituent may be substituted with another substituent.

Particularly, it is particularly preferable to refer to paragraph 0044 of Japanese Laid-Open Patent Publication No. 2009-191061, which disclosure is incorporated herein by reference.

Examples of the divalent organic group represented by A in the formula (OX-1) include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The above-mentioned substituent may be substituted with another substituent.

Among them, A in the formula (OX-1) is preferably an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group An alkylene group substituted with an alkenyl group (e.g., a vinyl group or an allyl group), an aryl group (e.g., a phenyl group, a p-tolyl group, a xylyl group, a cumene group, Anthryl group, phenanthryl group, styryl group) is preferable.

In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. The substituent may be the same as the substituent introduced into the substituted aryl group as a specific example of the aryl group which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferable in view of increasing the sensitivity and suppressing the coloring due to heating over time.

In the formula (OX-1), as a preferable structure of "SAr" formed from Ar in the formula (OX-1) and S adjacent thereto, reference may be made to the description of paragraph 0049 of JP-A No. 2009-191061 , The contents of which are incorporated herein by reference.

The oxime compounds can be referred to in paragraphs 0050 to 0106 of Japanese Laid-Open Patent Publication No. 2009-191061, the contents of which are incorporated herein by reference.

The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm and preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm and particularly preferably has a high absorbance at 365 nm and 455 nm.

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

Specific examples of the molar extinction coefficient of the compound include an ultraviolet visible spectrophotometer (Varian Carry-5 spectrophotometer), an ethyl acetate solvent at a concentration of 0.01 g / L .

When the photopolymerization initiator is contained in the coloring composition of the present invention, the content of the photopolymerization initiator is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 30 mass%, and still more preferably from 0.5 to 30 mass% 1 to 20% by mass. Within this range, more excellent sensitivity and pattern formability can be obtained.

The composition of the present invention may contain only one type of photopolymerization initiator or two or more types of photopolymerization initiators. When two or more kinds are included, the total amount is preferably in the above range.

When the coloring composition of the present invention has a pigment, the pigment dispersant may be used in combination with the purpose.

Examples of the pigment dispersant usable in the present invention include polymer dispersants such as polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, modified poly ), A surfactant such as polyoxyethylene alkylphosphoric acid ester, a polyoxyethylene alkylamine, an alkanolamine, and a pigment derivative, and the like can be given .

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on the structure.

Examples of the end-modified polymer having an anchor site on the surface of the pigment include a polymer having a phosphate group at the terminals described in JP-A-3-112992, JP-A-2003-533455, JP-A- -273191 and the like, a polymer having a partial skeleton of an organic dye described in JP-A No. 9-77994 and the like, a polymer having a heterocyclic ring, and the like. Further, a polymer having an anchor site (an acid group, a basic group, a partial skeleton of an organic dye, a heterocycle, etc.) introduced into two or more pigment surfaces at the polymer terminal described in Japanese Patent Application Laid-Open No. 2007-277514 is also excellent in dispersion stability desirable.

Examples of the graft polymer having an anchor portion on the surface of the pigment include a polyester dispersant and the like. Specifically, JP-A-54-37082, JP-A-8-507960 , Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668 and the like, reaction products of polyallylamine and polyester described in JP-A-9-169821 and the like, 10-339949, JP-A-2004-37986, WO2010 / 110491 and the like, copolymers of nitrogen atom monomers, JP-A-2003-238837, JP-A-2008-9426 Graft polymers having partial skeletons or heterocyclic rings of organic pigments described in JP-A-2008-81732 and the like, macromonomers described in JP-A-2010-106268 And the like can be mentioned acid group-containing copolymer of the monomer. Particularly, the amphoteric dispersing resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable from the viewpoints of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion Do.

A known macromonomer can be used as the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization. Macromonomer AA-6 (a macromonomer having a terminal group of methacryloyl AS-6 (polystyrene having a terminal group of methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (methyl methacrylate) Polylactic acid butyl ester whose terminal group is methacryloyl group), Flaccel FM5 (5-molar equivalent of 2-hydroxyethyl methacrylate-epsilon -caprolactone) manufactured by Daicel Chemical Industries, Ltd., FA10L (acrylic acid 2 - 10-molar equivalent of ε-caprolactone of hydroxyethyl), and polyester-based macromonomers described in JP-A-2-272009. Among them, polyester-based macromonomers having particularly good flexibility and good solvent-solubility are particularly preferable from the viewpoints of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, Polyester macromonomers represented by the polyester-based macromonomers described in JP-A-2-272009 are particularly preferable.

As block type polymers having anchor sites to the pigment surface, block type polymers described in JP-A-2003-49110 and JP-A-2009-52010 are preferable.

Examples of the pigment dispersant usable in the present invention are available as a commercial product. Specific examples thereof include DA-7301 manufactured by Goosumoto Kasei Co., Ltd., Disperbyk-101 (polyamide amine phosphate) manufactured by BYK Chemie, 107 (carboxylic acid ester ), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymeric copolymer) "," BYK-P104, P105 (Modified polyacrylate), 5010 (polyester amide), 5765 (polyacrylic acid), EFKA4047, 4050 to 4010 to 4165 (polyurethane resin), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (High molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno Co., Fluorene TG-710 (uretene oligomer) ", " Polyflow No. 50E, No. 300 (acrylic type (Aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA (dibutyl terephthalate), "DAPARON KS-860, 873SN, 874, # 2150 -725 ", " Demol RN, N (naphthalene sulfonic acid-formaldehyde polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ", " Homogenol L- &Quot; " Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ", " acetamin 86 (stearylamine acetate) ", Nippon Rubrizon Co., 28000, 32000, 38500 (graft polymer) ", manufactured by Nikko Chemicals Co., Ltd.), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Kawaken Fine Chemical Co., Ltd.," Hinoact T-8000E "manufactured by Kawaken Fine Chemicals Co., Article "Oh , &Quot; W001: cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ethers, polyoxyethylene nonylphenyl ethers, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters; and anionic surfactants such as "W004, W005, W017" Surfactant, "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450" manufactured by Morishita Sangyo Co., Ltd., "Disperse Aid" F68, L42, L44, L61, L64, F68, L72, and P95 of ADEKA manufactured by ADEKA under the trade name of "Disperse AID 8", "Disperse Aid 15, Disperse AID 9100" (Trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd.," F77, P84, F87, P94, L101, P103, F108, L121, It can be given.

These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersing agent. The pigment dispersant may be used in combination with an alkali-soluble resin together with an end-modified polymer having an anchor portion on the surface of the pigment, a graft-type polymer, and a block-type polymer. 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, and acidic cellulose derivatives having a carboxylic acid in the side chain. Particularly, a (meth) acrylic acid copolymer is preferable. The N-substituted maleimide monomer copolymer disclosed in JP-A No. 10-300922, the ether dimer copolymer disclosed in JP-A No. 2004-300204, the polymerizable group described in JP-A No. 7-319161 Is also preferable. Specifically, an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.

In the case of containing the pigment dispersant in the coloring composition, the total content of the pigment dispersant is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and more preferably 20 parts by mass per 100 parts by mass of the pigment To 40 parts by mass is more preferable.

The composition of the present invention may contain only one kind of pigment dispersing agent or two or more kinds of pigment dispersing agents respectively. When two or more kinds are included, the total amount is preferably in the above range.

Concretely, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 parts by mass to 100 parts by mass, more preferably in the range of 10 parts by mass to 80 parts by mass, based on 100 parts by mass of the pigment .

When the pigment derivative is used in combination, the amount of the pigment derivative to be used is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 3 to 20 parts by mass, based on 100 parts by mass of the pigment And most preferably in the range of 5 parts by mass to 15 parts by mass.

In view of curing sensitivity and color density, the total content of the colorant and the dispersant component in the coloring composition is preferably 50% by mass or more and 90% by mass or less, more preferably 55% by mass or more and 85% By mass or less, more preferably 60% by mass or more and 80% by mass or less.

<Alkali-soluble resin>

The coloring composition of the present invention preferably further contains an alkali-soluble resin.

The molecular weight of the alkali-soluble resin is not particularly limited, but Mw is preferably 5000 to 100,000. Further, it is preferable that Mn is 1000 to 20,000.

The weight average molecular weight of the compound used in the present invention is defined as a polystyrene reduced value by GPC measurement. For example, HLC-8220 (manufactured by TOSOH CORPORATION) was used as the weight average molecular weight and number average molecular weight, and TSKgel Super AWM-H (6.0 mm ID x 15.0 cm) By using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution.

As the alkali-soluble resin, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably an acrylic copolymer, a styrene-based copolymer as a main chain) . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group and the like, which are soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution And (meth) acrylic acid is particularly preferable. These acid groups may be only one kind, or two or more kinds.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And monomers having isocyanate groups such as isocyanatoethyl (meth) acrylate. The monomers for introducing these acid groups may be one kind or two or more kinds. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as " monomer for introducing an acid group & To be polymerized.

When an acid group is introduced as a monomer component capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of solvent at the time of producing the alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally .

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic anhydride copolymers, maleic acid copolymers and novolac resins, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to the polymer having a hydroxyl group. Particularly, 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, butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl , And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, Furfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like as the N-substituted maleimide monomer described in JP-A No. 10-300922 , N-phenylmaleimide, N-cyclohexylmaleimide and the like. In addition, these monomers copolymerizable with (meth) acrylic acid may be either one type alone or two or more types.

As the alkali-soluble resin, it is also preferable that the alkali-soluble resin includes a polymer (a) obtained by polymerizing a monomer component essentially containing a compound represented by the following formula (ED) (hereinafter may be referred to as "ether dimer"

[Chemical Formula 45]

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

As a result, the colored composition of the present invention can form a cured coating film having excellent heat resistance as well as transparency. Of the above-mentioned ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is not particularly limited and includes, for example, methyl, ethyl, n- Straight or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2' - [oxybis (Isopropyl) -2,2 '- [oxybis (methylene)] -2-propenoate, di (n-propyl) )] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (methylene)] bis- Di (tert-butyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (tert- Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) -2 Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di - methoxyethyl) -2,2 '- [oxy Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, dibenzyl- Bis (2-propenyl) bis [2-propenyl] biphenyl-2, 2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- (Methylene)] bis-2-propenoate, di (tert-butylcyclohexyl) -2,2 '- [oxybis Di (tricyclodecanyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamanthyl- Di (2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be either one kind or two or more kinds. The structure derived from the compound represented by the formula (ED) may be copolymerized with another monomer.

Further, in order to improve the crosslinking efficiency of the coloring composition in the present invention, it is preferable to use an alkali-soluble resin having a polymerizable group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful.

Examples of the polymer containing a polymerizable group include Polyne NR series (Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, Diamond Shamrock Co., Ltd.), Viscot R-264, KS Resist 106 (All manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series, Flackcell CF200 series (all manufactured by Daicel Chemical Industries, Ltd.) and Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) . As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a Acrylate-containing acrylic resin obtained by reacting a urethane-modified polymerizable double bond-containing acrylic resin obtained by reaction with an acrylic resin, an acrylic resin containing a carboxyl group, and a compound having an epoxy group and a polymerizable double bond together in the molecule Resin, an acid pendant epoxy acrylate resin, a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group and an isocyanate A resin obtained by reacting a compound having a polymerizable group, JP-A- 002-229207 and Japanese Unexamined Patent Application Publication No. 2003-335814, a resin obtained by basic treatment of a resin having an ester group having an ester group having a leaving group such as a halogen atom or a sulfonate group on? .

As the alkali-soluble resin, a multi-component copolymer composed of a (meth) acrylic acid benzyl / (meth) acrylic acid copolymer and a (meth) benzyl acrylate / (meth) acrylic acid / other monomer is suitable. (Meth) acrylic acid benzylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate copolymer disclosed in Japanese Patent Application Laid-open No. 7-140654 (Meth) acrylate / polystyrene 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 / benzyl methacrylate / meta Acrylic acid copolymers, and the like. Particularly preferred are copolymers of benzyl methacrylate / methacrylic acid and the like.

As the alkali-soluble resin, reference can be made to Japanese Patent Application Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of US Patent Application Publication No. 2012/0235099) Which is incorporated herein by reference.

In addition, the copolymer (B) described in paragraphs Nos. 0029 to 0063 described in JP-A-2012-32767 and the alkali-soluble resin used in the examples, and the copolymer described in paragraphs 0088 to 0098 of JP-A- The binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and the binder resin used in the examples of Japanese Laid-Open Patent Publication No. 2013-024934 To 0143 and binder resins used in the examples, paragraphs 0092 to 0098 of Japanese Laid-Open Patent Publication No. 2011-242752 and binder resins used in the examples, and Japanese Laid-Open Patent Publication No. 2012-032770, paragraph No. 0030 It is preferable to use the binder resin described in [0072]. The contents of which are incorporated herein by reference. More specifically, the following resins are preferable.

(46)

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, particularly preferably 70 mgKOH / g to 120 mgKOH / g.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 12% by mass relative to the total solid content of the coloring composition , And particularly preferably 3% by mass to 10% by mass.

The composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more kinds of alkali-soluble resins, and preferably contains two or more kinds, more preferably at least one type thereof has a polymerizable group. When two or more kinds are included, the total amount is preferably in the above range.

The coloring composition of the present invention may further contain other components such as a surfactant, a crosslinking agent, a polymerization inhibitor, an organic carboxylic acid, and an organic carboxylic acid anhydride in addition to the above-mentioned respective components, within the range not hindering the effect of the present invention .

<< Surfactant >>

To the coloring composition of the present invention, various surfactants may be added in order to further improve the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

Particularly, since the coloring composition of the present invention contains the fluorine-containing surfactant, the uniformity of the coating thickness and the liquid-repellency (liquid-repellency) can be improved in that the liquid property (particularly, fluidity) Can be further improved.

That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorine-containing surfactant is applied, the wettability of the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, Thereby improving the stability. Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine 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-containing surfactant having a fluorine content within this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-repellency, and the solubility in the coloring composition is also good.

Examples of the fluorochemical surfactant include Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101 (manufactured by Sumitomo 3M Co., Ltd.), F- , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Garas Co., Ltd.) .

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), poly Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Colloxystearate and sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 manufactured by BASF) Lubrizol Corporation) and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005 and W017 (manufactured by YUHO Co., Ltd.).

Examples of silicone based surfactants include fluorine-based surfactants such as TORAY Silicon DC3PA, TORAY Silicone SH7PA, TORAY Silicon DC11PA, TORAY Silicone SH21PA, TORAY Silicone SH28PA, TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4440 "," TSF- KP341 ", " KF6001 ", " KF6002 ", manufactured by Shin-Etsu Silicone Co., Ltd., BYK307, BYK323 and BYK330 manufactured by Big Chemie.

When the surfactant is contained in the coloring composition of the present invention, the addition amount of the surfactant is preferably from 0.001 mass% to 2.0 mass%, more preferably from 0.05 mass% to 1.0 mass%, based on the total mass of the coloring composition .

The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more kinds are included, the total amount is preferably in the above range.

<< Cross-linking agent >>

By using a crosslinking agent in addition to the coloring composition of the present invention, it is possible to further increase the hardness of the cured film obtained by curing the coloring composition.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples thereof include (a) an epoxy resin, (b) at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group (C) a phenol compound, naphthol compound or naphthol compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, wherein the phenol compound, the guanamine compound, the glycoluril compound or the urea compound, Hydroxyanthracene compounds. Among them, a polyfunctional epoxy resin is preferable.

Details of specific examples of crosslinking agents and the like can be found in paragraphs 0134 to 0147 of Japanese Laid-Open Patent Publication No. 2004-295116.

When the crosslinking agent is contained in the coloring composition of the present invention, the blending amount of the crosslinking agent is not particularly limited, but is preferably from 2 to 30 mass%, more preferably from 3 to 20 mass%, of the total solid content of the composition.

The composition of the present invention may contain only one type of crosslinking agent or two or more types of crosslinking agents. When two or more kinds are included, the total amount is preferably in the above range.

<< Polymerization inhibitor >>

In the coloring composition of the present invention, it is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the production of the coloring composition.

Examples of the polymerization inhibitor usable in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'- (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N- have.

When the polymerization inhibitor is contained in the coloring composition of the present invention, the addition amount of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the mass of the whole composition.

The composition of the present invention may contain only one kind of polymerization inhibitor or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

<< Organic carboxylic acid, organic carboxylic acid anhydride >>

The coloring composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1,000 or less and / or an organic carboxylic acid anhydride.

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid and an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid and methacrylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid A dicarboxylic acid such as acetic acid, adipic acid, pimelic acid, cyclohexane dicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid or fumaric acid, a tricarboxylic acid such as tricarbalic acid or aconitic acid, . Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid or phthalic acid, and a carboxylic acid in which a carboxyl group is bonded through a carbon bond from a phenyl group. Among these, particularly preferred are those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, for example, maleic acid, malonic acid, succinic acid and itaconic acid.

Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples thereof include acetic anhydride, anhydrous trichloroacetic acid, trifluoroacetic anhydride, anhydrous tetrahydrophthalic acid, Anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, anhydroglutaric acid, 1,2-cyclohexenedicarboxylic anhydride, n-octadecylsuccinic anhydride, anhydrous 5-norbornene-2,3-dicarboxylic acid And an aliphatic carboxylic acid anhydride. Examples of the aromatic carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrous naphthalic acid. Among these, particularly preferred are those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, and specifically, for example, maleic anhydride, succinic anhydride, citraconic anhydride and itaconic anhydride are preferable.

When the coloring composition of the present invention contains an organic carboxylic acid or an organic carboxylic acid anhydride, the addition amount of the organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% by weight, preferably 0.03 to 5% by weight, Preferably 0.05 to 3% by weight.

The composition of the present invention may contain only one kind of organic carboxylic acid and / or organic carboxylic acid anhydride, respectively, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remnant of the undissolved product of the coloring composition while maintaining high pattern adhesion.

In addition to the above, various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent and the like may be added to the coloring composition, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116, the contents of which are incorporated herein by reference.

The coloring composition of the present invention may contain a sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Application Laid-Open No. 2004-295116 or a thermal polymerization inhibitor described in paragraph 0081 of the same.

The composition of the present invention may contain only one kind or two or more kinds of each of the above components. When two or more kinds are included, the total amount is preferably in the above range.

&Lt; Preparation method of colored composition >

The coloring composition of the present invention is prepared by mixing the above-described components.

Further, at the time of preparing the coloring composition, each component constituting the coloring composition may be blended at one time, or each component may be dissolved and dispersed in a solvent and then blended continuously. In addition, the order of injection and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving and dispersing the entire components in a solvent at the same time. If necessary, the components may be appropriately mixed into two or more solutions and dispersions, .

The coloring composition prepared as described above is preferably filtered and separated by using a filter having a pore diameter of 0.01 to 3.0 m, more preferably a pore diameter of about 0.05 to 0.5 m, have.

When a pigment is incorporated into the composition of the present invention, it is preferable to use a washed pigment. By using the washed pigment, the foreign matter in the composition can be further reduced. A method for cleaning the pigment can be found in Japanese Laid-Open Patent Publication No. 2010-83997, paragraphs 0011 to 0099, the content of which is incorporated herein by reference.

The coloring composition of the present invention is preferably used for forming a colored layer of a color filter. More specifically, the coloring composition of the present invention is suitably used for forming a coloring pattern (coloring layer) of a color filter, because it can form a cured film having excellent heat resistance and color characteristics. Further, the coloring composition of the present invention is suitably used for forming a coloring pattern of a color filter used in a solid-state image pickup device (for example, CCD, CMOS, etc.) or an image display device such as a liquid crystal display . In addition, it can be suitably used for producing printing ink, inkjet ink, and paint. Among them, color filters for solid-state image pickup devices such as CCD and CMOS can be suitably used for production.

&Lt; Cured Film, Pattern Forming Method, Color Filter, and Manufacturing Method of Color Filter >

Next, the cured film, the pattern forming method and the color filter according to the present invention will be described in detail with reference to its manufacturing method.

The cured film of the present invention is obtained by curing the coloring composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method of the present invention, the coloring composition of the present invention is applied on a support to form a coloring composition layer, and unnecessary portions are removed to form a coloring pattern.

The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) of a color filter.

In the composition of the present invention, a color filter may be formed by pattern formation by the so-called photolithography method, or a pattern may be formed by a dry etching method.

That is, in the first method for producing a color filter of the present invention, a step of applying a coloring composition onto a support to form a coloring composition layer, a step of exposing the coloring composition layer to a pattern, A method of manufacturing a color filter including a step of forming a coloring pattern is exemplified.

A second method for producing a color filter of the present invention is a method for producing a color filter comprising the steps of applying a coloring composition onto a support to form a coloring composition layer and curing to form a colored layer, , A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask.

In the present invention, a photolithography method is more preferable.

The details of these will be described below.

Hereinafter, each step in the pattern forming method of the present invention will be described in detail with reference to a method of manufacturing a color filter for a solid-state imaging device, but the present invention is not limited to this method. Hereinafter, a color filter for a solid-state imaging device may be simply referred to as a " color filter ".

&Lt; Step of forming coloring composition layer >

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

As a support which can be used in the present step, for example, a solid substrate (e.g., a silicon substrate) provided with an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) A substrate for an imaging device can be used.

The coloring pattern in the present invention may be formed on the imaging element formation surface side (surface) of the substrate for the solid-state imaging element, or on the imaging element formation surface side (back surface).

The color pattern of the solid-state imaging element or the back surface of the substrate for a solid-state imaging element may be provided with a light-shielding film.

An undercoat layer may be provided on the support, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of the substance, or planarize the surface of the substrate. The undercoat layer may contain a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like, and these components may be appropriately selected from the components to be incorporated in the composition of the present invention desirable.

As a method of applying the coloring composition of the present invention onto a support, various coating methods such as slit coating, ink-jetting, spin coating, flexible coating, roll coating, screen printing and the like can be applied.

Drying (prebaking) of the coloring composition layer applied on the support can be performed at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds in a hot plate, an oven or the like.

<< Process of Exposure >>

In the exposure step, the coloring composition layer formed in the coloring composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. Thus, a cured film is obtained.

As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2 is preferably 50mJ / cm ² ~ 1000mJ / cm ^2, and more ^{preferably, 80mJ / cm 2 ~ 500mJ /} cm 2 in particular.

The thickness of the cured film (colored film) is preferably 1.0 占 퐉 or less, more preferably 0.1 占 퐉 to 0.9 占 퐉, and still more preferably 0.2 占 퐉 to 0.8 占 퐉.

By setting the film thickness to 1.0 m or less, high resolution and high adhesion can be obtained, which is preferable.

In addition, in this step, a cured film having a thin film thickness of 0.7 m or less can be suitably formed, and the obtained cured film is subjected to development processing in a pattern forming step described later to improve the developability, surface roughness , And a colored pattern excellent in the pattern shape can be obtained.

<< Development Process >>

Subsequently, by performing the alkali development treatment, the colored composition layer in the unexposed area in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured portion.

As the developing solution, an organic alkali developing solution which does not cause damage to the imaging element, circuit, etc. on the ground (base) is preferable. The developing temperature is usually 20 to 30 DEG C, and the developing time is conventionally 20 to 90 seconds. In order to remove the residues, it is sometimes carried out 120 to 180 seconds in recent years. Further, in order to further improve the removability of the residue, the step of removing the developing solution every 60 seconds and further supplying a new developing solution may be repeated a number of times.

Examples of the alkaline agent to be used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide And organic alkaline compounds such as trimethylbenzylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylbenzylammonium hydroxide, Is diluted with pure water to a concentration of 0.001 mass% to 10 mass%, preferably 0.01 mass% to 1 mass%, is preferably used as the developing solution.

As the developing solution, an inorganic alkali may be used, and examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like.

When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with pure water after development.

Subsequently, it is preferable to carry out a heat treatment (post-baking) after drying. If a multi-colored pattern is to be formed, a cured coating can be produced by repeating the above steps in order for each color. As a result, a color filter is obtained.

The post-baking is a post-development heat treatment for making the curing to be complete, and is generally subjected to a heat curing treatment at 100 캜 to 240 캜, preferably at 200 캜 to 240 캜.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), a high-frequency heater or the like so as to achieve the above-

&Lt; Case where pattern is formed by dry etching >

The dry etching can be performed by using an etching gas with the colored layer as the mask of the patterned photoresist layer. Specifically, a positive or negative radiation-sensitive composition is coated on the colored layer and dried to form a photoresist layer. In forming the photoresist layer, it is preferable to further perform the pre-baking treatment. Particularly, as the photoresist forming process, it is preferable that the post-exposure baking (PEB) and post-baking baking (post baking) are performed.

As the photoresist, for example, a positive radiation-sensitive composition is used. Examples of the positive radiation-sensitive composition include positive-working photoresists sensitive to radiation such as deep ultraviolet rays including ultraviolet rays (g line, h line, i line), excimer laser, electron beam, ion beam and X- Can be used as the positive resist composition. Among the radiation, g line, h line and i line are preferable, and among them, i line is preferable.

Specifically, as the positive radiation sensitive composition, a composition containing a quinone diazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinone diazide compound and an alkali-soluble resin has a structure in which a quinone diazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to generate a carboxyl group and, consequently, becomes alkali-soluble from an alkali- . This positive type photoresist has remarkably excellent resolving power and is used in the production of integrated circuits such as IC and LSI. As the quinone diazide compound, a naphthoquinone diazide compound can be mentioned. Commercially available products include, for example, " FHi622BC " (manufactured by FUJIFILM ELECTRONIC MATERIALS).

The thickness of the photoresist layer is preferably 0.1 to 3 占 퐉, more preferably 0.2 to 2.5 占 퐉, and still more preferably 0.3 to 2 占 퐉. The coating of the photoresist layer can be suitably performed by using the coating method in the above-described colored layer.

Subsequently, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a resist through-air group. The formation of the resist pattern can be performed by suitably optimizing the conventionally known photolithography technique without any particular limitation. A resist through-air group is provided in the photoresist layer by exposure and development, whereby a resist pattern as an etching mask used in the next etching is provided on the colored layer.

The exposure of the photoresist layer can be performed by irradiating the positive or negative radiation sensitive composition with g line, h line, i line or the like, preferably i line, through a predetermined mask pattern. After the exposure, the photoresist is removed in accordance with the region where the colored pattern is to be formed by developing with a developing solution.

Any developer which can dissolve the exposed portions of the positive resist and the uncured portions of the negative resist without affecting the colored layer containing the colorant can be used as the developer. For example, a combination of various organic solvents or an aqueous alkaline solution Can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving the alkaline compound in an amount of 0.001 to 10 mass%, preferably 0.01 to 5 mass%, is suitable. The alkaline compound may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Side chain, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. When an alkaline aqueous solution is used as a developing solution, cleaning treatment is generally performed with water after development.

Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that a through-air group is formed in the colored layer. Thus, a colored pattern is formed. The penetrating air group is provided on the colored layer in the form of a checkerboard. Therefore, the first coloring pattern formed by providing the through-air group in the colored layer has a plurality of rectangular colored first colored pixels in a checkerboard shape.

More specifically, dry etching is performed by dry etching the colored layer using the resist pattern as an etching mask. Representative examples of the dry etching are disclosed in Japanese Laid-Open Patent Application No. 59-126506, Japanese Laid-Open Patent Publication Nos. 59-46628, 58-9108, 58-2809, 57-148706, 61-41102 And the methods described in the respective publications.

The dry etching is preferably performed in the following manner, from the viewpoint of forming the cross-section of the pattern closer to a rectangle or further reducing the damage to the support.

(N ₂ ) and oxygen (N ₂ ) after the first-stage etching and a first-step etching in which a mixed gas of a fluorine-based gas and an oxygen gas (O ₂ ) It is preferable to use a mixed gas of gas (O ₂ ) and a mode including a second-step etching for performing etching to a region (depth) where the support is exposed, and an over-etching to be performed after the support is exposed. Hereinafter, a specific method of dry etching, first-stage etching, second-stage etching, and over-etching will be described.

Dry etching is performed by obtaining 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 respectively calculated. (2) The time for etching the desired thickness in the first-stage etching and the time for etching the desired thickness in the second-stage etching are respectively calculated. (3) The first-stage etching is performed according to the etching time calculated in (2) above. (4) The second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by end point detection, and the second-stage etching may be performed according to the determined etching time. (5) Overetching time is calculated for the total time of (3) and (4), and overetching is performed.

As the mixed gas used in the first step etching step, it is preferable to include a fluorine-based gas and oxygen gas (O ₂ ) from the viewpoint of processing the organic material as the etching film into a rectangular shape. In addition, the first-stage etching process can be performed by etching to a region where the support is not exposed, so that damage to the support can be avoided. The second etching step and the overetching step may be performed after the first etching step has been performed to a region where the support is not exposed by the mixed gas of the fluorine gas and the oxygen gas, , A mixed gas of nitrogen gas and oxygen gas is preferably used for the etching treatment.

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 inhibit the rectangularity by the etching treatment in the first step etching step. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching step and the etching amount in the second-step etching step) is preferably in the range of more than 0% and not more than 50% 20% is more preferable. The etching amount refers to an amount calculated as the difference between the thickness of the film to be etched remaining and the film thickness before etching.

Further, it is preferable that the etching includes an over-etching treatment. The overetching treatment is preferably performed by setting an overetching ratio. It is preferable that the overetching ratio is calculated from the first etching treatment time. The overetching ratio can be arbitrarily set. It is preferably 30% or less of the etching treatment time in the etching step, more preferably 5 to 25% in terms of etching resistance of the photoresist and maintaining the rectangularity of the etched pattern , And particularly preferably 10 to 15%.

Subsequently, the resist pattern (i.e., etching mask) remaining after etching is removed. The removal of the resist pattern preferably includes a step of applying a removing liquid or a solvent to the resist pattern to bring the resist pattern into a removable state and a step of removing the resist pattern by using washing water.

Examples of the step of applying a releasing liquid or a solvent to the resist pattern to remove the resist pattern include a step of applying at least a peeling liquid or a solvent on the resist pattern and stagnating the resist pattern for a predetermined time to perform paddle development . The time for stucking the peeling liquid or the solvent is not particularly limited, but is preferably several tens of seconds to several minutes.

The step of removing the resist pattern using the washing water includes, for example, a step of spraying washing water onto the resist pattern from a spraying nozzle or a shower-type spraying nozzle to remove the resist pattern. As the washing water, pure water can be preferably used. As the injection nozzle, there can be mentioned a spray nozzle including the entire support within its spray range, and a spray nozzle having a movable range of its movable range including the entire support. When the spray nozzle is of the movable type, the resist pattern can be more effectively removed by moving the cleaning fluid from the center of the support to the end of the support more than twice during the process of removing the resist pattern.

The peeling liquid generally contains an organic solvent, but may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol compound, 4) an ether or acetal compound, 5) a ketone or aldehyde compound, Based compounds, 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride-based compounds, 9) phenolic compounds, 10) nitrogen-containing compounds, 11) sulfur compounds, and 12) fluorine compounds. The release liquid preferably contains a nitrogen-containing compound, and more preferably includes an uncyclosed nitrogen compound and a cyclic nitrogen compound.

The non-cyclic nitrogen compound is preferably a non-cyclic nitrogen compound having a hydroxyl group. Specific examples thereof include mono isopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine , Triethanolamine and the like. Monoethanolamine, diethanolamine and triethanolamine are preferable, and monoethanolamine (H ₂ NCH ₂ CH ₂ OH) is more preferable. Examples of cyclic nitrogen compounds include isoquinoline, imidazole, N-ethylmorpholine, epsilon -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, , pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, pyrrolidine, Pyridine, 2,4-lutidine, 2,6-lutidine and the like, preferably N-methyl-2-pyrrolidone and N-ethylmorpholine, 2-pyrrolidone (NMP).

It is preferable that the exfoliating liquid contains a non-cyclic nitrogen compound and a cyclic nitrogen compound. Among them, as the non-cyclic nitrogen compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, , And as the cyclic nitrogen compound, at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine is more preferable, and monoethanolamine and N-methyl- It is more preferable to include them.

In the case of removing with the peeling liquid, the resist pattern formed on the first colored pattern may be removed, and even when the deposit as the etching product adheres to the side wall of the first colored pattern, the deposit may not be completely removed . The sediment means that the etching product adheres to the side wall of the colored layer and is deposited.

As for the exfoliation liquid, the content of the non-cyclic nitrogen compound is 9 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the exfoliant, and the content of the cyclic nitrogen compound is not less than 65 parts by mass and not less than 70 parts by mass By mass or less. It is preferable that the exfoliation liquid is a mixture of a non-cyclic nitrogen compound and a cyclic nitrogen compound diluted with pure water.

Further, the manufacturing method of the present invention may have a known process as a manufacturing method of a color filter for a solid-state image pickup device, as necessary, as the other processes described above. For example, the coloring composition layer forming step, the exposing step, and the pattern forming step described above may be performed, and then, if necessary, a curing step of curing the formed coloring pattern by heating and / or exposure may be included.

In addition, when the coloring composition of the present invention is used, for example, there is a case where clogging of nozzles and piping in the dispensing device discharge portion, contamination by deposition, sedimentation and drying of the coloring composition or pigment into the applicator occurs . Therefore, in order to efficiently clean the contamination caused by the coloring composition of the present invention, it is preferable to use the solvent relating to the present composition described above as a cleaning liquid. Further, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, The cleaning liquids described in JP-A-2006-291191, JP-A-2007-2101, JP-A-2007-2102 and JP-A-2007-281523 are also suitable as a cleaning liquid for the coloring composition of the present invention Can be used to make.

Among these, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.

These solvents may be used alone or in combination of two or more. When mixing two or more species, it is preferable to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) is particularly preferably 60/40. Further, in order to improve the permeability of the cleaning liquid to the contaminants, the surfactant relating to the present composition described above may be added to the cleaning liquid.

Since the color filter of the present invention uses the coloring composition of the present invention, it is possible to perform exposure with excellent exposure margin, and the formed color pattern (colored pixel) has excellent pattern shape, and the roughness of the pattern surface And the residue in the developing portion is suppressed, so that the color characteristic is excellent.

The color filter of the present invention can be suitably used for a solid-state image pickup device such as a CCD and a CMOS, and is particularly suitable for a CCD or a CMOS of high resolution exceeding one million pixels. The color filter for a solid-state imaging device 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.

The thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 占 퐉 or less, more preferably 1.0 占 퐉 or less, and even more preferably 0.7 占 퐉 or less.

The size (pattern width) of the coloring pattern (coloring pixel) is preferably 2.5 占 퐉 or less, more preferably 2.0 占 퐉 or less, and particularly preferably 1.7 占 퐉 or less.

<Solid-state image sensor>

The solid-state image pickup device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as the configuration includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode composed of polysilicon or the like are formed on a support, and on the photodiode and the transfer electrode, And a device shielding film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. The device protective film is provided with the color filter for solid- Filter.

Further, it may be a configuration having the light-converging means (for example, a microlens or the like hereinafter) on the device protective film and below the color filter (near the support) or a configuration having the light-

The color filter of the present invention can be used not only for the solid-state image pickup device but also for an image display device such as a liquid crystal display device and an organic EL display device, and is particularly suitable for use in a liquid crystal display device. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with good display characteristics and excellent display characteristics.

For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, " Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention 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 may be used in a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, " Color TFT liquid crystal display (published by Kyoritsu Shootpan Co., Ltd., 1996) ". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

Further, the color filter in the present invention can be used in a color-filter on array (COA) method which is bright and high definition. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. In the color filter of the present invention, a COA type liquid crystal display (liquid crystal display) having a high resolution and excellent long-term durability is used because of its excellent color purity, light transmittance, Device can be provided. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described in, for example, page 43 of " EL, PDP, and LCD display technology and the latest trend in the market " (published by Toray Research Center Research Division, 2001).

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These items are described in, for example, "Market of Liquid Crystal Display Materials and Chemicals," issued by Shimadaira Co., Ltd., 1994, "2003," 2003 Present condition and future prospect of liquid crystal- (Published by Fuji Chimerasoken Co., Ltd., 2003). &Quot;

Regarding the backlight, it is described in SID meeting Digest 1380 (2005) (A. Konno et al), Monthly Display December 2005, pages 18-24 (Yamazaki Shimaya), 25-30 pages (Yagi Takaaki) .

When the color filter according to the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube. In addition, LED light sources (RGB-LEDs) of red, By using a backlight, it is possible to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Synthesis Example of Pigment Polymer

The following Formulas (1) to (4) are included in the preferable form (A1) of the above-mentioned colorant multimer. The following dyestuffs 5 are included in the above-mentioned preferable form (A2) of the dye multimer. The following xanthine 6 is included in a preferable form (A3) of the above-mentioned dye multimer. The following dyestuffs 7 and 8 are included in the preferred form (A4) of the above-mentioned dye multimer.

&Lt; Synthesis of xanthine 1 >

(47)

Rhodamine B (20.0 g, 41.8 mmol) was dissolved in 125 g of chloroform, and 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling with an ice bath. Thereafter, the mixture was heated at an external temperature of 65 占 폚 for 3 hours and then cooled to 20 占 폚. While cooling with an ice bath, 9.8 g (75.2 mmol) of 2-hydroxyethyl methacrylate was added and 30.8 g did. After the internal temperature was adjusted to 20 캜 and stirred for 3 hours, 100 g of chloroform was added and the mixture was separated by water, and then the chloroform layer was concentrated. The resulting concentrate was added to 100 mL of methanol, and 16.4 g (41.8 mmol) of tetrabutylammonium trifluoromethylsulfonate was added. The mixture was partitioned between ethyl acetate (200 mL) and water (100 mL), and the ethyl acetate layer was concentrated to obtain 18.0 g of monomer X.

Methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as "PGMEA"), (23.3 g), and the mixture was heated to 80 占 폚 in a nitrogen atmosphere. To this solution was added a monomer X (8.2 g), methacrylic acid (1.075 g), dodecylmercaptan (0.255 g), dimethyl 2,2'-azobis (isobutyrate) (0.58 g) and PGMEA (23.3 g) was added dropwise over 3 hours. Thereafter, the mixture was stirred for 4 hours, then heated to 90 占 폚, stirred with heating for 2 hours, and then cooled to obtain a PGMEA solution of the intermediate (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL and re-dissolved. After blow drying at 40 DEG C for 2 days, 7.9 g of a colorant multimer (xanthan 1) was obtained.

The weight average molecular weight (Mw) of the dye multimer (Zanthane 1) confirmed by GPC measurement was 7,700. Further, the acid value was 37 mgKOH / g by titration using a 0.1 N aqueous sodium hydroxide solution.

&Lt; Synthesis of xanthine 2 to xanthine 4 >

(Xanthan 2 to Xanthan 4) were synthesized by carrying out the same operations except that the counter anions in the monomer X in Synthesis Example 1 were changed to those described in the following table.

(48)

&Lt; Synthesis of xanthine 5 >

The following monomers (55 mol% of xanthan monomer and 45 mol% of methacrylic acid) were copolymerized to synthesize xanthan gum 5.

(49)

C. I. Acid Red 289 27.4 g (41.8 mmol) was dissolved in 125 g of chloroform, and 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling with an ice bath. Thereafter, the mixture was cooled to 20 deg. C heated at an external temperature of 65 deg. C for 3 hours, and then 9.0 g (75.2 mmol) of 4-aminostyrene was added while cooling with an ice bath, and 30.8 g (304 mmol) of triethylamine was added. The mixture was stirred at room temperature for 3 hours, and 100 g of chloroform was added thereto. The mixture was separated by water, and the chloroform layer was concentrated to obtain 15.0 g of monomer Z. At this time, 10.0 g of the monomer Z2 was obtained from the aqueous layer.

Monomer Z (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g) and PGMEA (23.3 g) were added to a three-necked flask and heated to 80 占 폚 in a nitrogen atmosphere. To this solution was added a monomer Z (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), dimethyl 2,2'-azobis (isobutyrate) (0.58 g) and PGMEA (23.3 g) was added dropwise over 4 hours. Thereafter, the mixture was stirred for 4 hours, then heated to 93 ° C, and heated and stirred for 2 hours and then cooled to obtain a PGMEA solution of the intermediate (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL and re-dissolved. After blow drying at 40 DEG C for 2 days, 7.4 g of a colorant multimer (xanthan 5) was obtained.

The weight average molecular weight (Mw) of the dye multimer (Zanthien 5) confirmed by GPC measurement was 6,500. Further, by titration using a 0.1 N aqueous sodium hydroxide solution, the acid value was 38 mgKOH / g.

61 mol% of xanthan monomer Y and 39 mol% of methacrylic acid

(50)

(41.8 mmol) of Rhodamine B and 24.3 g (41.8 mmol) of a potassium salt of the following polymerizable anion were subjected to salt exchange in 200 ml of methanol, and 1 L of water was added, followed by extraction with 500 ml of chloroform and concentration to obtain 25 g of monomer Y lost.

(51)

To the three-necked flask, monomer Y (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g) and PGMEA (23.3 g) were added and heated to 80 ° C under a nitrogen atmosphere. To this solution was added a monomer Y (8.2 g), methacrylic acid (1.075 g), dodecylmercaptan (0.255 g), dimethyl 2,2'-azobis (isobutyrate) (0.58 g) and PGMEA (23.3 g) was added dropwise over 5 hours. Thereafter, the mixture was stirred for 5 hours, then heated to 93 ° C, and heated and stirred for 2 hours, followed by cooling to obtain a PGMEA solution of the intermediate (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL and re-dissolved. After blow drying at 40 캜 for 2 days, 4.8 g of a pigment multimer (xanthine 6) was obtained.

The weight average molecular weight (Mw) of the dye multimer (Zanten 6) confirmed by GPC measurement was 6,900.

&Lt; Synthesis of xanthine 7 >

The following monomers (xanthan monomer Z2 (51 mol%) and methacrylic acid (49 mol%)) were copolymerized to synthesize xanthan 7.

(52)

In a three-necked flask, monomer Z2 (8.2 g), methacrylic acid (0.46 g), dodecylmercaptan (0.255 g) and propylene glycol 1-monomethylether 2-acetate Quot; PGMEA ") (23.3 g) was added, and the mixture was heated to 80 DEG C under a nitrogen atmosphere. To this solution was added a monomer Z2 (8.2 g), methacrylic acid (1.075 g), dodecylmercaptan (0.255 g), dimethyl 2,2'-azobis (isobutyrate) (0.58 g) and PGMEA (23.3 g) was added dropwise over 3 hours. Thereafter, the mixture was stirred for 4 hours, then heated to 90 占 폚, stirred with heating for 2 hours, and then cooled to obtain a PGMEA solution of the intermediate (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL and re-dissolved. After blow drying at 40 캜 for 2 days, 7.8 g of a colorant multimer (xanthine 7) was obtained.

The weight average molecular weight (Mw) of the dye multimer (Zanten 7) confirmed by GPC measurement was 8,200. Further, by titration using a 0.1 N aqueous sodium hydroxide solution, the acid value was 38 mgKOH / g.

&Lt; Synthesis of xanthine 8 >

(Copolymer of the following monomers)

(Xanthone 8) was obtained in accordance with the process for producing the titration compound (A-1) described in paragraph 0165 of Japanese Patent Application Laid-Open No. 2011-242752. The weight average molecular weight (Mw) of the dye multimer (Zanten 7) confirmed by GPC measurement was 15,000.

(53)

Preparation of coloring composition

Preparation of blue pigment dispersion

Blue Pigment Dispersion 1 was prepared as follows.

(Zirconia beads 0.3 mm diameter) was mixed with 10.0 parts of CI Pigment Blue 15: 6 (blue pigment, average particle size 55 nm), 3.0 parts of Disperbyk 111 as a pigment dispersant, 70.0 parts of PGMEA and 17.0 parts of cyclohexanone, For 3 hours to prepare a pigment dispersion. Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) with a pressure-reducing mechanism. This dispersion treatment was repeated ten times to obtain a blue pigment dispersion 1 (CI Pigment Blue 15: 6 dispersion, pigment concentration 10% by mass) used for the coloring composition of Example or Comparative Example.

Preparation of Example 0

The following components were mixed, dispersed and dissolved to obtain the coloring composition of Example 0.

In addition, prior to preparing Example 0, toluene and water in the system were removed by distillation of the solvent used and drying agent, and the dyes and pigments were washed with distilled water and dried repeatedly to remove Na and K ions in the system did. Other materials such as monomers were purified before use to remove impurities (toluene, Na, K ions, etc.) before preparation.

The above-mentioned blue pigment dispersion 1 390.0 parts

Alkali-soluble resin 1 (copolymer of 55 mol% benzyl methacrylate and 45 mol% methacrylic acid, weight average molecular weight 10,000, hereinafter referred to as "B1") 3.8 parts

Alkali-soluble resin 2 (the following resin, weight average molecular weight: 11,000, hereinafter referred to as "B2") 1.0 part

(54)

· Curable compound (6-functional monomer of the following structure, hereinafter referred to as "m1")

9.0 part

(55)

8.5 parts of a photopolymerization initiator (hereinafter referred to as " I-1 ", described in Japanese Patent Laid-Open Publication No. 2011-158654)

(56)

· 25 parts by mass of colorant (Zanten 1) solids

0.2 part of a fluorine-based surfactant (F-475, manufactured by DIC Corporation)

· PGMEA 260 parts

The results of measurement of the concentrations of the following components in the composition of Example 0 are shown.

Water content: not more than 0.01% by mass

Toluene concentration: 0.005 ppm or less

Na ion concentration: 0.005ppm or less

K ion concentration: 0.005 ppm or less

The water content was measured by the Karl Fischer method in accordance with a known method. Specifically, the water content of the measurement data was measured using a Karl Fischer moisture meter (KF-06 manufactured by Mitsubishi Chemical Holdings), and the water content was measured with the water content / mass of measurement data × 100.

The toluene concentration was determined by preparing a calibration curve by gas chromatography according to a known method. In the present invention, after each material of the composition was vacuum-dried to confirm that the toluene content was 0.005 ppm or less, a composition having a different toluene concentration was prepared by separately adding toluene at the time of preparation of the composition.

To the composition of Example 0 was added water, toluene, and an ion source of Na (specifically prepared by preparing a methanol solution of sodium chloride and adding it), a K ion source (specifically, a methanol solution of potassium bromide was prepared, To prepare a sample of Examples 1 to 6.

The compositions of Examples 7 to 77 and Comparative Examples 1 to 16 were also prepared in the same manner as in Example 0 except that the dye-multimer, the curable compound (monomer) and the photopolymerization initiator were changed as shown in the following table.

The curable compound (monomer (m-2))

(57)

The curable compound (monomer (m-3))

(58)

The curable compound (monomer (m-4))

[Chemical Formula 59]

Photopolymerization initiator (I-2, OXE-02 manufactured by BASF)

(60)

Photopolymerization initiator (I-3, Irgacure 907, BASF)

(61)

&Lt; Evaluation of long-term aging stability &

The initial viscosities (Vi) of the compositions obtained in the Examples and Comparative Examples were measured, and the viscosity was kept at 23 deg. C for 100 days in a sealed container. Further, the viscosity (Vd) after aging was measured. | Vi-Vd | / Vi 占 100% was calculated, and the evaluation was made based on the value. A criterion of 3 or more is practically preferable. The results are shown in the following table.

6: Viscosity change rate is 0.5% or less (particularly good)

5: Viscosity change rate is higher than 0.5% and less than 3% (good)

4: Viscosity change rate is higher than 3% and less than 7% (slightly better)

3: Viscosity change rate is higher than 7% and lower than 8% (within allowable range)

2: Viscosity change rate is higher than 8% and below 12% (out of acceptable range)

1: Viscosity change rate is higher than 12% (out of acceptable range)

Fabrication of Color Filter by Coloring Composition

&Lt; Pattern formation >

Each of the color compositions of the examples and comparative examples prepared as described above was coated on a glass substrate to form a colored composition layer (coating film). Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 0.6 탆.

&Lt; Long term light resistance under low oxygen concentration >

Using a SX75F (manufactured by Suga Shikeki Co., Ltd.), a light resistance tester of a xenon lamp light source (in which oxygen supply was cut off and became in a low oxygen state), the film formation product (pattern) obtained in the examples and the comparative example was covered, 500 lux for 2000 hours to conduct a light resistance test.

The color difference (? E * ab) before and after irradiation was measured by MCPD-2000 manufactured by Otsuka Denshi Co., Ltd. and evaluated. A criterion of 3 or more is practically preferable. The results are shown in the following table.

6: 0.5% or less (especially good)

5: higher than 0.5% and not higher than 1% (good)

4: 1% higher than 2% (slightly better)

3: Higher than 2% and lower than 3% (within allowable range)

2: higher than 3% and less than 5% (out of acceptable range)

1: Greater than 5% (out of acceptable range)

Each of the radiation sensitive compositions obtained above was applied onto a silicon wafer so that the film thickness after coating was 0.6 占 퐉 and then heated on a hot plate at 100 占 폚 for 2 minutes to obtain a colored composition layer.

Foreign matter having a size of 1.0 탆 or more was counted on the substrate on which the colored composition layer was formed by using a defect evaluation apparatus ComPLUS (manufactured by Applied Materials, Inc.).

This evaluation was carried out immediately after the preparation of the coloring composition layer and one month after freezing (-18 캜), and the foreign matter increase rate was evaluated on the basis of the following criteria.

The foreign matter increase rate was calculated as (number of foreign matter after one month of freezing / number of foreign matter immediately after preparation). A criterion of 3 or more is practically preferable. The results are shown in the table.

(Criteria)

6: Less than 1.1

5: 1.1 or more and less than 1.3

4: 1.3 to less than 1.5

3: 1.5 to less than 2.0

2: 2.0 or more and less than 3.0

1: 3.0 or higher

(Preparation of silicon wafer with undercoating layer)

Coated with a resist CT-4000L solution (FUJIFILM ELECTRONIC MATERIALS CO., LTD., An undercoat transparent) onto a silicon wafer using a spin coater so as to have a film thickness of 0.1 mu m, and dried by heating at 220 DEG C for 1 hour, And a silicon wafer with an undercoat layer was obtained.

(Production of coloring pattern)

The coloring compositions of Examples and Comparative Examples were applied on a silicon wafer with an undercoat layer by a spin coat method so that the film thickness after application was 0.6 占 퐉 and then heated on a hot plate at 90 占 폚 for 2 minutes to obtain a colored composition layer .

Subsequently, the obtained coloring composition layer was exposed at 1.0 m through the mask at 300 mJ / cm < ² > using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Subsequently, the exposed coloring composition layer was subjected to paddle development at 23 DEG C for 60 seconds using a 1.0% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, rinsing was carried out with a spin shower, and further washed with pure water to obtain a colored pattern.

The line width of the obtained color pattern was observed with a line-of-sight SEM (trade name: S-7800H, manufactured by Hitachi, Ltd.). The difference between the maximum value and the minimum value of the line width in one pixel in the case where the delay time was 72 hours was determined by measuring arbitrary 10 points in the wafer and obtaining an average value. Also, in the case where the delay time was 0 hour, the average value in both Examples and Comparative Examples was < 0.02 mu m.

A criterion of 3 or more is practically preferable. The results are shown in the table.

(Criteria)

6: less than 0.02 탆 (best)

5: 0.02 탆 or more and less than 0.04 탆 (good)

4: 0.04 m or more and less than 0.06 m (slightly better)

3: not less than 0.06 μm and not more than 0.10 μm (within allowable range)

2: 0.10 μm or more and less than 0.20 μm (not permitted)

1: 0.20μm or more (not allowed)

&Lt; Evaluation of defect after humidity test (Evaluation of foreign matter increase rate) >

The compositions of Examples and Comparative Examples were coated on a silicon wafer so that the film thickness after coating was 0.6 占 퐉 and heated on a hot plate at 100 占 폚 for 2 minutes to obtain a coloring composition layer. Thereafter, the entire surface was subjected to i-line exposure at an exposure dose of 1000 mJ / cm < ² > and further heated at 200 DEG C / 10 minutes on a hot plate to obtain an initial sample.

With respect to the initial sample, a sample subjected to humidity resistance for 408 hours under the condition of 110 캜 and 85% RH was used as a sample after the humidity resistance test.

For each of the samples, a defect evaluation apparatus ComPLUS (manufactured by Applied Materials, Inc.) was used to count foreign objects having a size of 1.0 m or more. The foreign matter increase rate was evaluated based on the following criteria.

The foreign matter increase rate was calculated by (number of foreign objects in the sample after humidity resistance / number of foreign objects in the initial sample). A criterion of 3 or more is practically preferable. The results are shown in the table.

(Criteria)

6: Less than 1.1

5: 1.1 or more and less than 1.3

4: 1.3 to less than 1.5

3: 1.5 to less than 2.0

2: 2.0 or more and less than 3.0

1: 3.0 or higher

<Long-term thermal cycle test>

After the compositions of the examples and comparative examples were stored under the following temperature conditions, the rate of increase of the coated object was evaluated.

Temperature condition (1): 30 DEG C / 72hr

Temperature condition (2): 23 DEG C / 72hr

Temperature condition (3): 5 DEG C / 72hr

After two repetitions in the order of the temperature condition (1), the temperature condition (2) and the temperature condition (3), the coated object was evaluated.

&Lt; Evaluation of coated foreign matters &

The coloring composition was coated on a silicon wafer so that the film thickness after coating was 0.6 占 퐉, and then heated on a hot plate at 90 占 폚 for 2 minutes to obtain a coloring composition layer.

Foreign matter having a size of 2.0 탆 or more was counted on the substrate on which the coloring composition layer was formed using a defect evaluation apparatus ComPLUS (manufactured by Applied Materials, Inc.).

The foreign matter increase rate was calculated as (number of foreign substances after the heat cycle test / number of foreign substances immediately after preparation) and evaluated according to the following classification.

(Criteria)

6: Less than 1.1 (best)

5: 1.1 or more and less than 1.3 (good)

4: 1.3 to less than 1.5 (slightly fine)

3: 1.5 to less than 2.0 (not allowed)

2: 2.0 or more and less than 4.0 (not allowed)

1: 4.0 or higher (not allowed)

[Table 3]

[Table 4]

[Table 5]

From the results shown in the above table, it was found that, when at least one of the sodium ion concentration and the potassium ion concentration in the coloring composition is 0.1 to 10 ppm, it is difficult to generate foreign matter when placed for a long time under a low-temperature environment.

Further, it has been found that good water resistance can be maintained even when the water content in the coloring composition is kept at a low oxygen concentration for a long period of time by the water content of 0.1 to 5 mass%.

In addition, it was found that the uniformity of the line width of the colored pattern can be maintained even when the delayed time-keeping is performed for a long time because the concentration of toluene in the coloring composition is 1 to 13 ppm.

In Examples 70 to 77, it was found that any evaluation results other than the evaluation of the long-term thermal cycle test were satisfactory.

Claims

(A) a colorant composition containing a pigment multimer having a partial structure and an anion site derived from a xanthine pigment having a cation moiety and (B) a solvent,
The pigment oligomer (A) comprises a partial structure represented by the following general formula (J '),
Wherein at least one of a sodium ion concentration and a potassium ion concentration in the coloring composition is 0.1 to 10 ppm.
... The general formula (J ')
(In the formula (J '), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, , And represents an integer of 0 to 5.)

The method according to claim 1,
Wherein the toluene concentration in the coloring composition is 1 to 13 ppm.

delete

The method according to claim 1 or 2,
The anion portion is bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion, tetra aryl borate anions, 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 is 1 to 4), or PF _n2 R ^P _(6-n2) ^- (wherein R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms and n2 is an integer of 1 to 6 ). &Lt; / RTI >

The method according to claim 1 or 2,
Lt; RTI ID = 0.0 > phthalocyanine < / RTI > pigment.

The method according to claim 1 or 2,
And a photopolymerization initiator.

The method according to claim 1 or 2,
&Lt; / RTI > further comprising a curable compound.

The method according to claim 1 or 2,
Wherein at least one of a sodium ion concentration and a potassium ion concentration in the coloring composition is 3 to 7 ppm.

The method according to claim 1 or 2,
A coloring composition for forming a colored layer of a color filter.

A cured film obtained by curing the coloring composition according to claim 1 or 2.

A step of forming a coloring composition layer by applying the coloring composition according to claim 1 or 2 on a support, a step of exposing the coloring composition layer in a pattern shape, and a step of forming a coloring pattern by developing the unexposed portion Of the color filter.

A step of applying the coloring composition according to claim 1 or 2 on a support to form a coloring composition layer and curing to form a colored layer,
A step of forming a photoresist layer on the colored layer,
A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and
And dry etching the colored layer using the resist pattern as an etching mask.

A color filter having the cured film according to claim 10.

A solid-state imaging device having the color filter according to claim 13.

An image display apparatus having the color filter according to claim 13.

delete

The method according to claim 1,
The colorant composition (A) contains a repeating unit represented by the following general formula (a1-1).

... In general formula (a1-1)
(In formula (a1-1), X ¹ represents a group forming a main chain, L ¹ represents a single bond or a divalent linking group, and DyeI represents a group having a structure represented by the following formula (J ').

... The general formula (J ')
(In the formula (J '), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, , And represents an integer of 0 to 5.)