TWI615673B - Colored composition, cured film, color filter, method for manufacturing color filter, solid-state image sensing device, and image display device - Google Patents

Abstract

The present invention provides a colored composition, a cured film, a color filter, a method for manufacturing a color filter, a solid-state imaging device, and an image display device that can maintain the line width uniformity of a colored pattern even after being left for a long time. The coloring composition of the present invention contains (A) a pigment polymer and (B) a solvent, and (A) the pigment polymer has a partial structure derived from an xanthracene pigment having a cationic site and an anionic site, and the coloring composition The toluene concentration is 0.001ppm ~ 10ppm.

Description

Coloring composition, hardened film, color filter, color filter Manufacturing method, solid-state imaging element and image display device

The present invention relates to a colored composition and a cured film using the same. The present invention also relates to a color filter having a cured film, a method for manufacturing the color filter, a solid-state imaging element having a color filter, and an image display device.

One of the methods for manufacturing a color filter used in a liquid crystal display device, a solid-state imaging device, and the like is a pigment dispersion method. The pigment dispersion method is a method in which a pigment is dispersed in various photosensitive compositions. The photosensitive composition uses a photolithography method to produce a color filter. That is, a colored composition is applied to a substrate using a spin coater, a roll coater, or the like, and dried to form a coating film, and the coated film is subjected to pattern exposure and development to obtain colored pixels. The operation is repeatedly performed only with a desired degree of hue, thereby producing a color filter.

The method is stable to light or heat due to the use of a pigment, and is patterned by a photolithography method, so that positional accuracy can be sufficiently ensured, and it is widely used as a color suitable for manufacturing a color display. Filter, etc.

Patent Document 1 discloses that a colored photosensitive composition containing a dye or a pigment is used when producing a color filter. Patent Document 2 discloses that a dye polymer containing a xanthene skeleton as a partial structure of a dye site is used to improve developability. In addition, Patent Document 2 also discloses a combination of a cationic site and an anionic site in a dye polymer.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-268242

[Patent Document 2] Japanese Patent Laid-Open No. 2012-32754

Here, it is known that when a composition containing the following dye polymer is used to form a colored pattern, if it is left for a long time, the line width uniformity of the colored pattern tends to be poor, and the dye polymer has a source Part of the structure of the xanthracene dye having a cation site and an anion site.

The objective of this invention is to solve the said subject, and to provide the coloring composition which can maintain the line width uniformity of a coloring pattern even if it is left for a long time.

The present inventors have found that the above-mentioned problem can be solved by formulating a small amount of toluene in a composition containing a pigment polymer having an oxanthracene pigment derived from a cationic site. Partial structure and anion site.

Specifically, the above-mentioned problem was solved by the following means <1>, preferably means <2> to means <13>.

<1> A coloring composition containing (A) a pigment polymer and (B) a solvent, and (A) the pigment polymer having a partial structure derived from an xanthracene pigment having a cationic site and an anionic site, and a colored composition The toluene concentration was 0.001ppm ~ 10ppm.

<2> The colored composition according to <1>, wherein the water content in the colored composition is 0.005 ppm to 3 ppm.

<3> The coloring composition according to <1> or <2>, wherein at least one of a sodium ion concentration and a potassium ion concentration in the coloring composition is 0.01 ppm to 20 ppm.

<4> The coloring composition according to any one of <1> to <3>, wherein the anion site is an anion site having a low nucleophilicity.

<5> The coloring composition according to any one of <1> to <4>, further containing a phthalocyanine pigment.

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

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

<8> The coloring composition according to any one of <1> to <7>, which is used for forming a coloring layer of a color filter.

<9> A cured film obtained by curing the colored composition according to any one of <1> to <8>.

<10> A method for manufacturing a color filter, comprising the steps of: applying the coloring composition according to any one of <1> to <8> to a support to form a coloring composition layer; A step of exposing the colored composition layer in a pattern; and a step of developing and removing an unexposed portion to form a colored pattern.

<11> A method for producing a color filter, comprising the steps of applying the coloring composition according to any one of <1> to <8> to a support to form a coloring composition layer, and A step of forming a colored layer by hardening; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by performing exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask A step of dry etching the colored layer by masking.

<12> A color filter, which is a color filter having a cured film according to <9> or produced by the method for producing a color filter according to <10> or <11> Color filters.

<13> A solid-state imaging element or an image display device including the color filter according to <12>.

According to the present invention, it is possible to provide a coloring composition that can maintain the line width uniformity of a coloring pattern even when left for a long time.

The description of the constituent elements of the present invention described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the description of the group (atomic group) in the present specification, the descriptions that are not substituted and unsubstituted include groups that do not have a substituent, and also include groups that have a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

The "radiation" in this specification refers to, for example, a bright line spectrum of a mercury lamp, extreme ultraviolet rays (Extreme Ultraviolet (EUV) light) represented by an excimer laser, X-rays, electron beams, and the like. The term "light" as used in the present invention refers to actinic rays or radiation. The term "exposure" as used in this specification means, unless otherwise specified, not only exposure with far-ultraviolet rays, X-rays, and EUV light represented by mercury lamps and excimer lasers, but also drawing with particle beams such as electron beams and ion beams. Also included in the exposure.

The numerical range indicated by "~" in this specification refers to a range including numerical values described before and after "~" as a lower limit value and an upper limit value.

As used herein, the term "total solid content" refers to the total mass of components obtained by removing the solvent from the total composition of the composition.

In addition, in this specification, "(meth) acrylate" means both or both of acrylate and methacrylate, and "(meth) acryl" means both or any of acrylic and methacrylic acid, "(Meth) acrylfluorenyl" means both or any of acrylmethyl and methacrylmethyl.

In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in this specification refers to a compound that is distinguished from oligomers and polymers and has a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

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

In this specification, the term "step" refers not only to an independent step, but even when it cannot be clearly distinguished from other steps, it is included in the term as long as the intended function of the step can be achieved.

<Coloring composition>

The coloring composition of the present invention (hereinafter also referred to as the composition of the present invention) contains (A) a pigment polymer and (B) a solvent, and the coloring composition is characterized in that (A) the pigment polymer has a source A partial structure of a xanthracene pigment having a cationic site (hereinafter sometimes referred to as a "pigment structure") and an anionic site, and the toluene concentration in the composition of the present invention is 0.001 ppm to 10 ppm.

According to the present invention, the line width of the colored pattern can be maintained even when left for a long time. The so-called long-term standing refers to the lengthening of the film after the film is formed using the coloring composition. Time left until i-ray exposure.

In the present invention, the problem caused by the long-term standing is solved by preparing a small amount of toluene. Although the mechanism is speculative, by blending a small amount of toluene, the compatibility between the cationic site in the pigment structure and the hydrophobic component in the composition is good, and phase separation does not occur even if it is left for a long time, which can be maintained. The line width of the pattern is uniform. On the other hand, when the toluene concentration is high, toluene aggregates a hydrophobic component (for example, a hardening compound or the like) in the composition to a degree more than necessary. In the present invention, the problem is appropriately solved by setting the toluene concentration to the range.

In the present invention, for example, even when the leaving time is set to 2 days or more and 0.3% by mass of tetramethylammonium hydroxide is used as the developing solution after exposure, the line width of the pattern can be maintained uniform.

In the present invention, the toluene concentration in the composition is preferably 0.005 ppm to 10 ppm, preferably 0.01 ppm to 3 ppm, more preferably 0.1 ppm to 3 ppm, and even more preferably 0.5 ppm to 2 ppm.

In addition, the composition of the present invention preferably has a water content in the composition of 0.005% to 3% by mass, more preferably 0.01% to 1% by mass, and still more preferably 0.05% to 0.15% by mass.

By setting the water content to 3% by mass or less, it is possible to more effectively suppress the occurrence of separation between the cationic site and the anionic site in the pigment polymer. For a film formed in a state where the cationic site and the anionic site are not easily separated, at low oxygen concentrations, the pigment-excited free radicals are not easily trapped by oxygen, and the pigment is hardly decomposed.

In addition, by setting the water content to 0.005 mass% or more, the distance between the cation site and the anion site in the pigment polymer will not be too close, so it is difficult to cause energy migration or electron migration during photoexcitation, which makes the pigment more difficult break down. As a result, good light resistance can be maintained even when left for a long time at a low oxygen concentration.

In particular, when light is irradiated at 10,000 lux for 1 week or more under a low oxygen concentration, good light resistance can be maintained.

The composition of the present invention preferably has at least one of sodium ion concentration and potassium ion concentration in the composition satisfying 0.01 ppm to 20 ppm, more preferably 0.01 ppm to 10 ppm, still more preferably 0.1 ppm to 5 ppm, and even more preferably 0.5 ppm. ~ 2ppm. It is particularly preferred that both the sodium ion concentration and the potassium ion concentration satisfy the ranges, respectively.

By setting the sodium ion concentration and potassium ion concentration to 20 ppm or less, it is possible to suppress the ion exchange reaction between cations in the pigment polymer and at least one of sodium and potassium ions in the composition, and further improve the pigment structure and composition. The compatibility of other components in the composition (such as resin, monomer, solvent, etc.) can effectively suppress phase separation in the composition. As a result, even if a composition is placed in a low-temperature environment (for example, in a refrigerated storage state) to be formed into a film, it is difficult to generate foreign matter. In addition, by setting the sodium ion concentration and potassium ion concentration to be 0.01 ppm or more, it is possible to effectively suppress the generation of foreign matter caused by an excessively high compatibility between the pigment structure and other components.

From the viewpoint of long-term moisture resistance performance, the composition of the present invention preferably has a solid content voltage retention ratio of 10% to 80%, more preferably 30% to 60%.

In addition, in the present invention, by setting the structure as described above, a colored composition having a small rate of change in viscosity over a long period of time can be obtained. For example, even at low temperatures (5 ° C or less) After 3 months or more, the rate of change in viscosity can also be reduced.

In addition, in the present invention, when the product is left for a long period of time at various temperatures (for example, -30 ° C to 150 ° C) and / or high humidity (for example, relative humidity is 80% or more), a small foreign matter generation rate can be obtained. Coloring composition. For example, even in a case where it is left for more than one month in a low-temperature (5 ° C or lower) environment or a case where it is left for more than two weeks in an environment of 85 ° C and 85% RH, the foreign matter generation rate can be reduced.

The composition of the present invention can be preferably used for forming a colored layer of a color filter. The coloring composition of the present invention preferably contains a curable compound and a pigment. Examples of the sclerosing compound include a polymerizable compound and an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group), and may be appropriately selected depending on the application or the production method. Furthermore, it is preferable that the coloring composition of this invention contains a photoinitiator.

For example, when the colored layer is formed by photoresist, the colored composition of the present invention preferably contains a pigment polymer, a solvent, an alkali-soluble resin as a curable compound, a pigment, and a photopolymerization initiator. It may further contain components such as a surfactant.

When the colored layer is formed by dry etching, it is preferable to contain a pigment polymer, a solvent, a polymerizable compound as a curable compound, a pigment, and a photopolymerization initiator. It may further contain components such as a surfactant.

<< (A) Pigment polymer >>

Pigment polymers include structures such as dimers, trimers, and polymers. The pigment polymer functions as a colorant in the coloring composition of the present invention.

The dye polymer has a partial structure derived from a xanthracene dye having a cationic site and an anionic site. The preferred form of the pigment polymer includes the following forms state.

(A1) A pigment polymer containing a repeating unit having a counter anion site having a partial structure derived from an xanthracene dye having a cation site.

(A2) A pigment polymer containing the following repeating unit and the pigment structure having an anionic site, the repeating unit having a partial structure derived from an xanthracene pigment having a cationic site.

(A3) A pigment polymer containing a monomer having a partial structure derived from an xanthracene pigment having a cationic moiety and a repeating unit having a counter anion moiety.

(A4) A pigment polymer having other cation and anion sites in the pigment polymer.

Hereinafter, each aspect will be described in detail.

<<< Form of (A1) >>>

<<<< Counterbalance anion site >>>>

The counter anion site of the pigment polymer (A) is preferably non-nucleophilic. The so-called non-nucleophilicity refers to the property that the pigment is not subjected to nucleophilic attack due to heating.

The counter anion may be an organic anion or an inorganic anion, and an organic anion is preferred. Examples of the anion include those described in paragraph No. 0075 of Japanese Patent Laid-Open No. 2007-310315, and the contents are incorporated into the specification of the present application.

Preferred include: bis (sulfo acyl) acyl imide anion, tris (sulfo acyl) 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, n1 represents 1 to 4) and PF _n2 R ^P _(6-n2) ^- (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms) , N2 represents an integer from 1 to 6), more preferably selected from the group consisting of bis (sulfofluorenyl) fluorenimide anion, tris (sulfofluorenyl) methylate anion, and tetraarylborate anion, further preferably bis ( Sulfonyl) fluorenimide anion. By using such a counter anion, the effect of the present invention tends to be more effectively exhibited.

The bis (sulfofluorenyl) fluorenimide anion preferably has a structure represented by the following general formula (AN-1).

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

X ¹ and X ² each independently represent a fluorine atom or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, preferably a fluorine atom or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, and more preferably a carbon number 1 A perfluoroalkyl group of ~ 10, more preferably a perfluoroalkyl group of 1 to 4 carbon atoms, and particularly preferably a trifluoromethyl group.

The tris (sulfofluorenyl) methylate anion preferably has a structure of the following general formula (AN-2).

[Chemical 2]

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

X ³ , X ^4, and X ⁵ each independently have the same meaning as X ¹ and X ² , and the preferred ranges also have the same meaning.

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

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

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further 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. In the case of having 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 sulfonylamino group, a nitro group, and the like are preferable. The halogen atom and the alkyl group are more preferably a fluorine atom and an alkyl group, and even more preferably a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably a phenyl group having a halogen atom and / or a halogen atom-containing alkyl group, and further preferably a phenyl group having a fluorine atom and / or a fluorine-containing alkyl group. .

Another counter anion portion is preferably ^{_{-B (CN) n1 (OR a}} ) 4-n1 (R a represents alkyl having 1 to 10 carbon atoms or an aryl group having 6 to 10, n1 represents an integer of 1 to 4) . R ^{a which} is an alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R ^{a which is} an aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.

n1 is preferably 1 to 3, and more preferably 1 to 2.

Furthermore, the counter anion site is further preferably -PF ₆ R ^P _(6-n2) ^- (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n 2 represents an integer of 1 to 6). R ^{P is} preferably a fluorine atom-containing alkyl group having 1 to 6 carbon atoms, more preferably a fluorine-containing alkyl group having 1 to 4 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.

The mass of each molecule of the counter anion site is preferably 100 to 1,000, and more preferably 200 to 500.

The pigment polymer may contain only one kind of counter anion part, and may contain two or more kinds.

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

[Chemical 4]

[Chemical 6]

[Chemical 7]

<<<< Pigment structure >>>>

The so-called pigment structure in the present invention is a partial structure derived from a xanthracene pigment having a cationic site, and refers to a number of pigments which can be obtained by removing hydrogen atoms from a specific pigment (hereinafter also referred to as a pigment compound) which can form a pigment structure Polymer link Conjugated chains or dendrimer cores. These details will be described below.

The pigment structure is not particularly limited as long as it is a structure derived from a xanthracene pigment having a cationic site, and various structures including known ones can be applied.

The dye polymer (A) includes those having a partial structure derived from an xanthracene compound represented by the following general formula (J) as a partial structure of a dye site.

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

Desirable substituents of R ⁸¹ to R ⁸⁴ and R ⁸⁵ in the general formula (J) are the same as those listed for the substituent group A described later.

In the general formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ in the case where m is 2 or more may be independently bonded to each other to form a 5-member, 6-member, or 7-member saturation. Ring or 5 member, 6 member or 7 member unsaturated ring. In the case where the formed 5-membered, 6-membered or 7-membered ring is a group that can be further substituted, it may be substituted with the substituents described in R ⁸¹ to R ⁸⁵ and substituted with two or more substituents. In the case of substituent substitution, these substituents may be the same or different.

In the general formula (J) R ⁸¹ and R ^82, R ⁸³ and R ^84, and m is 2 or more case R ⁸⁵ independently of one another are bonded to each other to form a 5 having no substituent group, and 6 In the case of a 7-membered saturated ring or a 5-membered, 6-membered, and 7-membered unsaturated ring, a 5-membered, 6-membered, and 7-membered saturated ring having no substituent, or a 5-membered, 6-membered, and 7-membered unsaturated ring Examples of the ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, and a ring. The hexene ring, benzene ring, pyridine ring, pyrazine ring, and pyridazine ring (preferably, benzene ring and pyridine ring) are mentioned.

Particularly preferably, 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. In addition, R ^{85 is} preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamido group, a carboxyl group, and a fluorenyl group, and more preferably a sulfo group, a sulfonamido group, and a carboxyl group. Hydrazone. R ^{85 is} preferably bonded to an adjacent portion of the carbon bonded to the xanthracene ring. The substituents of the phenyl group of R ⁸¹ and R ⁸⁴ are particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamido group, and a carboxyl group.

The compound having a xanthracene skeleton represented by the general formula (J) can be synthesized by a method described in the literature. Specific applications include "Tetrahedron Letters" (2003, vol.44, No.23, pages 4355 ~ 4360), and "tetrahedron" (2005, vol.61, No.12, pages 3097 ~) 3106).

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

[Table 2]

[Chemical 10]

Regarding the dye polymer, the hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A as long as it does not deviate from the gist of the present invention.

Substituent group A: Substituents which the dye polymer may have include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, Nitro, carboxyl, alkoxy, aryloxy, silyloxy, heterocyclooxy, fluorenyloxy, carbamoyloxy, amine (including alkylamino, aniline), fluorenylamino, Aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino or arylsulfonylamino, mercapto, alkylthio, aromatic Thio, heterocyclic thio, sulfamoyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfinyl or arylsulfinyl, fluorenyl, aryloxycarbonyl, Alkoxycarbonyl, carbamoyl, arylazo or heterocyclic azo, fluorenimine, phosphino, phosphinyl, phosphinyloxy, phosphinylamine Group, silane group, etc. Details are described below.

Examples include: a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a straight-chain or branched alkyl group (a straight-chain or branched substituted or unsubstituted alkyl group, preferably 1 to 1 carbon atoms) 30 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl Group, third butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl (preferably, substituted or unsubstituted carbon having 3 to 30 carbon atoms) Substituted cycloalkyl, such as cyclohexyl, cyclopentyl, and polycyclic alkyl, such as bicycloalkyl (preferably substituted or unsubstituted bicycloalkyl having 5 to 30 carbon atoms, such as bicyclo [ 1.2.2] Heptane-2-yl, bicyclic [2.2.2] octane-3-yl) or tricyclic alkyl groups. Monocyclic cycloalkyl, bicycloalkyl are preferred , Particularly preferably monocyclic cycloalkyl), linear or branched alkenyl (linear or branched substituted or unsubstituted alkenyl, preferably alkenyl having 2 to 30 carbon atoms, such as vinyl , Allyl, isoprenyl, geranyl, oleyl), cycloalkenyl (preferably substituted or unsubstituted cycloalkenyl having 3 to 30 carbon atoms, for example, 2-cyclic Penten-1-yl, 2-cyclohexen-1-yl, polycyclic alkenyl, such as bicyclic alkenyl (preferably substituted or unsubstituted bicyclic alkenyl having 5 to 30 carbon atoms, such as bicyclic [ 2.2.1] hept-2-en-1-yl, bicyclic [2.2.2] oct-2-en-4-yl) or tricyclic alkenyl, particularly preferably monocyclic cycloalkenyl), Group (preferably substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl), aryl (preferably 6 to 30 carbon atoms) Substituted or unsubstituted aryl groups, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecylamidoaminophenyl), heterocyclic (preferably 5-7 members) Substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-forming atom is selected from carbon atom, nitrogen atom and sulfur atom and has A heterocyclic group of at least one hetero atom of a nitrogen atom, an oxygen atom, and a sulfur atom, and further preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furanyl, 2- Thienyl, 2-pyridyl, 4- Pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxyl, alkoxy (preferably substituted or unsubstituted alkane having 1 to 30 carbon atoms) Oxygen, such as methoxy, ethoxy, isopropoxy, tertiary butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy (preferably 6 to 30 carbon atoms) Substituted or unsubstituted aryloxy, such as phenoxy, 2-methylphenoxy, 2,4-di-tertiarypentylphenoxy, 4-tert-butylphenoxy, 3 -Nitrophenoxy, 2-tetradecanylamidoaminophenoxy), silyloxy (preferably a silanol having 3 to 20 carbon atoms, such as trimethylsilyloxy, third butyl Dimethylsilyloxy), heterocyclicoxy (preferably substituted or unsubstituted heterocyclicoxy having 2 to 30 carbon atoms, and the heterocyclic part is preferably described in the heterocyclic group described above) Heterocyclic moiety such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), fluorenyloxy (preferably methylamino, substituted or unsubstituted carbon number 2-30) A substituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formamyloxy, acetamyloxy, tris Methyl ethoxy, stearyl oxy, benzyl oxy, p-methoxyphenyl carbonyloxy), carbamoyloxy (preferably substituted or unsubstituted with 1 to 30 carbon atoms) Substituted amine formamyloxy, such as N, N-dimethylamine formamyloxy, N, N-diethylamine formamyloxy, morpholinyl carbonyloxy, N, N- Di-n-octylaminocarbonyloxy, N-n-octylaminemethaneoxy), alkoxycarbonyloxy (preferably substituted or unsubstituted alkoxycarbonyloxy having 2 to 30 carbon atoms) Groups such as methoxycarbonyloxy, ethoxycarbonyloxy, tertiary butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy (preferably 7 to 30 carbon atoms) Substituted or unsubstituted aryloxycarbonyloxy, such as phenoxycarbonyloxy, p-methoxyphenoxy Carbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy), amine (preferably amine, substituted or unsubstituted alkylamino having 1 to 30 carbon atoms, carbon 6 ~ 30 substituted or unsubstituted arylamino groups, heterocyclic amino groups of 0-30 carbons, such as amine, methylamino, dimethylamino, aniline, N-methyl-aniline Group, diphenylamino group, N-1,3,5-triazin-2-ylamino group), fluorenylamino group (preferably methylamidoamino group, substituted or unsubstituted carbon number 1-30) Substituted alkylcarbonylamino groups, substituted or unsubstituted arylcarbonylamino groups having 6 to 30 carbon atoms, such as methylamidoamino, ethylamidoamino, trimethylethylamidoamino, Laurylamino, benzamidoamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino (preferably substituted or 1-30 carbon atoms) Unsubstituted aminocarbonylamino, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinylcarbonylamino ), Alkoxycarbonylamino (preferably substituted or unsubstituted alkoxycarbonylamino having 2 to 30 carbon atoms, such as methoxycarbonylamino, Oxycarbonylamino, tertiary butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino (preferably carbon number 7 ~ 30 substituted or unsubstituted aryloxycarbonylamino group, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m-n-octyloxyphenoxycarbonylamino group), amine sulfonate Fluorenylamino (preferably substituted or unsubstituted aminesulfonamidoamino having 0 to 30 carbon atoms, such as sulfamoranylamino, N, N-dimethylaminosulfonamidoamine , N-n-octylaminosulfonylamino), alkylsulfonylamino or arylsulfonylamino (preferably substituted or unsubstituted alkylsulfonyl having 1 to 30 carbon atoms) Fluorenylamino, substituted or unsubstituted aryl having 6 to 30 carbon atoms Sulfonylamino, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methyl Phenylsulfonylamino), mercapto, alkylthio (preferably substituted or unsubstituted alkylthio having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio) ), Arylthio (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclicthio (A substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms is preferred, and the heterocyclic portion is preferably the heterocyclic portion described in the heterocyclic group described above, such as 2-benzothiazole thio Group, 1-phenyltetrazol-5-thio), sulfamoyl group (preferably substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylaminosulfonyl group , N- (3-dodecyloxypropyl) aminosulfonyl, N, N-dimethylaminesulfonyl, N-ethylsulfanylsulfonyl, N-benzylaminosulfonyl Group, N- (N'-phenylaminomethylamido) aminosulfonyl), sulfo, alkylsulfinyl, or arylsulfinyl (preferably substituted or Unsubstituted Sulfinyl sulfenyl, 6 ~ 30 substituted or unsubstituted arylsulfinyl sulfinyl, such as methylsulfinyl sulfinyl, ethylsulfinyl sulfinyl, phenylsulfinyl sulfinyl, p-methylbenzene Alkylsulfinyl), alkylsulfinyl or arylsulfonyl (preferably substituted or unsubstituted alkylsulfonyl having 1 to 30 carbon atoms, substituted or unsubstituted in 6 to 30 carbon atoms) Substituted arylsulfonyl, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), fluorenyl (preferably methylfluorenyl, carbon number 2 ~ 30 substituted or unsubstituted alkylcarbonyl groups, 7 ~ 30 carbon substituted or unsubstituted arylcarbonyl groups, such as ethylfluorenyl, trimethylethylfluorenyl, 2-chloroethylfluorenyl, Stearyl, benzene Formamyl, p-n-octyloxyphenylcarbonyl), aryloxycarbonyl (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxy Carbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl), alkoxycarbonyl (preferably substituted or unsubstituted alkoxycarbonyl having 2 to 30 carbon atoms, such as methoxy Carbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), carbamate (preferably substituted or unsubstituted carbamate having 1 to 30 carbon atoms, For example, carbamoyl, N-methylaminoformamyl, N, N-dimethylaminoformamyl, N, N-di-n-octylamineformamyl, N- (methylsulfonyl) Carbamoyl), arylazo or heterocyclic azo (preferably substituted or unsubstituted aryl azo having 6 to 30 carbon atoms, substituted or unsubstituted having 3 to 30 carbon atoms) A substituted heterocyclic azo group (the heterocyclic portion is preferably the heterocyclic portion described in the heterocyclic group described above), such as phenylazo, p-chlorophenylazo, 5-ethyl Thio-1,3,4-thiadiazol-2-ylazo), fluorenimine (preferably substituted or unsubstituted carbon number 2-30) Sulfonium imine, such as N-succinimide, N-phthalimide, imidene, phosphine (preferably substituted or unsubstituted phosphine having 2 to 30 carbon atoms, such as dimethyl Phosphinyl, diphenylphosphino, methylphenoxyphosphino), phosphinyl (preferably substituted or unsubstituted phosphinyl having 2 to 30 carbon atoms, for example, phosphinyl, dioctyl Oxyphosphino, diethoxy phosphino), phosphino oxy (preferably substituted or unsubstituted phosphino oxy with 2-30 carbon atoms, such as diphenoxyphosphine Oxy, dioctyloxyphosphinooxy), phosphinoamino (preferably substituted or unsubstituted phosphinoamino with 2-30 carbon atoms, such as dimethoxyphosphine Aminoamino, dimethylaminophosphinoamino), silyl (preferably substituted or unsubstituted silyl having 3 to 30 carbon atoms, such as trimethyl Silyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

A part of the hydrogen atom in the functional group having a hydrogen atom in the functional group may be substituted with any one of the 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. Specifically, Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an ethylfluorenylaminosulfonyl group, and a benzamidineaminosulfonyl group.

<Structure of Pigment Polymer>

The pigment polymer (A) used in the coloring composition of the present invention is not particularly limited, but preferably contains at least one of the repeating units represented by the following general formula (a1-1) and general formula (a1-2) Or a pigment polymer represented by the general formula (a1-3). The repeating unit represented by the general formula (a1-1) may contain only one kind, or two or more kinds, in one kind of pigment polymer. Furthermore, as described later, other repeating units may be contained.

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

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

(In the general formula (a1-1), X ¹ represents a group forming a main chain, and L ¹ represents a single bond or a divalent linking group. DyeI represents a pigment structure having a cationic site)

Hereinafter, the 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, it means the part which forms the repeating unit equivalent to the main chain formed in a polymerization reaction. X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, and is particularly preferably a linking group represented by the following (XX-1) to (X-24), and more preferably From the (meth) acrylic linking chains represented by (XX-1) and (XX-2), the styrene-based linking chains represented by (XX-10) to (XX-17), and (XX-24) Among the vinyl-based linking chains shown, further preferred are (meth) acrylic-based linking chains represented by (XX-1) and (XX-2) and styrene-based linking chains represented by (XX-11).

(XX-1) ~ (XX -24) , a * represents the portion indicated in the link to L ^1.

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

[Chemical 12]

In the general formula (a1-1), L ¹ represents a single bond or a divalent linking group. When L ¹ represents a divalent linking group, the divalent linking group represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, methylene, ethylene, trimethylene, ethylene Propyl, butylene, etc.), substituted or unsubstituted arylene (e.g., phenylene, naphthyl, etc.) having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic linking group,- CH = CH-, -O-, -S-, -C (= O)-, -CO _2- , -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -and will A linking group formed by linking two or more of these. L ^{1 is more} preferably a single bond or an alkylene group, and even more preferably a single bond or-(CH ₂ ) n- (n is an integer of 1 to 5). Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The divalent linking group represented by L ¹ may be a group capable of forming an ionic or coordination bond with DyeI. In this case, either an anionic group or a cationic group may be used.

Anionic groups include _{^{-COO -, -PO 3 H -,}} -SO 3 -, -SO 3 NH -, -SO 3 N - CO- and the like, preferably _{^{-COO -, -PO 3 H -,}} -SO ₃ ^-.

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

When L ¹ in the case of a group having ionic bond or a coordinate bond may be formed DyeI, L ¹ may be an anionic portion _{^{(-COO -, -SO 3 -,}} -O - , etc.) or cationic DyeI portion has ( The onium cation or metal cation, etc.) are bonded.

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

A pigment polymer containing a repeating unit represented by the general formula (a1-1) can be synthesized by: (1) a method of synthesizing a monomer having a pigment residue by addition polymerization; (2) using A polymer having a highly reactive functional group such as an isocyanate group, an acid anhydride group, or an epoxy group, and a functional group (hydroxyl, Primary or secondary amine groups, carboxyl groups, etc.).

In addition polymerization, well-known addition polymerization (radical polymerization, anionic polymerization, and cationic polymerization) can be applied. Among them, especially when synthesis is performed by radical polymerization, the reaction conditions can be stabilized without causing pigments. Structural decomposition is better. In the radical polymerization, known reaction conditions can be applied.

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

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

[Chemical 13]

[Chemical 14]

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

Next, the pigment polymer represented by general formula (a1-2) will be described in detail.

(In the general formula (a1-2), L ³ represents a single bond or a divalent linking group. DyeIII represents a pigment structure having a cationic site. M represents 0 or 1)

In the general formula (a1-2), L ³ represents a single bond or a divalent linking group. The divalent linking group represented by L ³ may be preferably a substituted or unsubstituted linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene, ethylidene, and trimethylene). Groups, propyl, butyl, etc.), substituted or unsubstituted arylenes (e.g., phenyl, naphthyl, etc.) having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic linkages Group, -CH = CH-, -O-, -S-, -NR- (R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C (= O)-, -SO- , -SO _2- , and a linking group formed by linking two or more of these.

m represents 0 or 1, preferably 1.

Specific examples of the divalent linking group represented by L ³ in the general formula (a1-2) are described below, but L ^{3 of the} present invention is not limited to these specific examples. The part indicated by * indicates a connection part with DyeIII or the like.

[Chemical 17]

A pigment polymer containing a repeating unit represented by the general formula (a1-2) is synthesized by sequential polymerization. The sequential polymerization includes polyaddition (for example, a reaction of a diisocyanate compound and a diol, a reaction of a diepoxy compound and a dicarboxylic acid, a reaction of a tetracarboxylic dianhydride and a diol, etc.), and polycondensation (for example, Reaction of dicarboxylic acid and diol, reaction of dicarboxylic acid and diamine, etc.). Among them, especially in the case of synthesizing by a multi-addition reaction, the reaction conditions are stable, and the pigment structure is not decomposed, which is preferable. In the sequential polymerization, known reaction conditions can be applied.

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

<< Pigment polymer represented by general formula (a1-3) >>

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

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

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

In the general formula (a1-3), in the case where n is 2, the divalent linking group represented by L ⁴ may be preferably a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, Methylene, ethylene, trimethylene, propyl, butyl, etc.), substituted or unsubstituted aryl (e.g., phenyl, naphthyl, etc.) having 6 to 30 carbon atoms, Substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, -NR- (R each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group),- C (= O)-, -SO-, -SO ₂ -and a linking group formed by linking two or more of these.

Examples of n-valent linking groups where n is 3 or more include substituted or unsubstituted arylene groups (1,3,5-phenylene, 1,2,4-phenylene, 1,4,5,8 -Naphthyl, etc.), a heterocyclic linking group (e.g., 1,3,5-triazinyl, etc.), a linking group formed by using an alkylene linking group as the center core and substituting the divalent linking group .

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

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

[Chemical 22]

The pigment polymer containing at least one of the repeating units represented by the general formula (a1-1) and the general formula (a1-2) and the pigment polymer represented by the general formula (a1-3) contain the general formula ( a pigment polymer of a repeating unit represented by a1-1), a pigment polymer containing a repeating unit represented by general formula (a1-2), and a pigment polymer represented by general formula (a1-3) Since the partial structure of the pigment is linked by a covalent bond in the molecular structure, the coloring composition containing the pigment multimer is excellent in heat resistance. Therefore, when a colored composition is applied to the pattern formation which has a high temperature process, it is effective at suppressing the color shift to another adjacent colored pattern, and it is preferable. In addition, the compound represented by the general formula (a1-1) is particularly preferable because it is easy to control the molecular weight of the dye polymer.

<< Other functional groups and repeating units >>

The dye polymer may have other functional groups in addition to the dye structure of the dye polymer. Examples of the other functional group include a polymerizable group, an acid group, and an alkali-soluble group.

In addition, the pigment polymer can also be used in addition to the repeating unit containing the pigment structure. Contains other repeating units. Other repeating units 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 polymer may contain other repeating units in addition to the repeating units represented by the general formulae (a1-1) to (a1-3). The other repeating units may contain only one kind, or two or more kinds in one pigment polymer.

The dye polymer may have other functional groups in the dye polymer represented by the general formulae (a1-1) to (a1-3). These details will be described below.

<<< Polymerizable group of the dye polymer (A) >>>

The dye polymer preferably contains a polymerizable group. The polymerizable group may contain only one kind, or may contain two or more kinds.

Regarding the polymerizable group, the pigment structure may contain a polymerizable group, and other portions may contain a polymerizable group. In the present invention, the pigment structure preferably contains a polymerizable group. By setting it as such a structure, there exists a tendency for heat resistance to improve.

In the present invention, a state in which the polymerizable group is contained in portions other than the pigment structure is also preferable.

As the polymerizable group, a known polymerizable group which can be crosslinked by radical, acid, and heat can be used, and examples thereof include a group containing an ethylenically unsaturated bond and a cyclic ether group (epoxy group, oxa group). Cyclobutane), methylol and the like are particularly preferably a group containing an ethylenically unsaturated bond, more preferably a (meth) acrylfluorenyl group, and even more preferably a glycidyl (meth) acrylate and (Meth) propyl of (meth) acrylic acid 3,4-epoxy-cyclohexyl methyl ester Alkenyl.

The polymerizable group is preferably contained in the dye polymer as a repeating unit having a polymerizable group, and more preferably is contained as a repeating unit having an ethylenically unsaturated bond. That is, an example of a preferred embodiment of the dye polymer is a state in which the dye polymer contains a repeating unit containing a dye-containing monomer and a repeating unit containing a polymerizable group. Repeating units containing ethylenically unsaturated bonds.

There are the following methods for introducing a polymerizable group: (1) a method of introducing a polymerizable group by modifying a pigment polymer using a polymerizable group-containing compound, and (2) a pigment monomer and a polymerizable group-containing compound A method of performing copolymerization to introduce a polymerizable group and the like. The details are described below.

(1) A method for introducing a polymerizable group by modifying a pigment polymer with a polymerizable group-containing compound: A method of modifying a pigment polymer with a polymerizable group-containing compound and introducing a polymerizable group may be omitted. Known methods are used with particular limitation. For example, from the viewpoint of production, the following methods are preferred: (a) a method of reacting a carboxylic acid possessed by the pigment polymer with an unsaturated bond-containing epoxy compound, and (b) a method of reacting the pigment polymer with A method of reacting a hydroxyl group or an amine group with an unsaturated bond-containing isocyanate compound, and (c) a method of reacting an epoxy compound included in the dye polymer with an unsaturated bond-containing carboxylic acid compound.

(a) The unsaturated bond-containing epoxy compound in the method of reacting a carboxylic acid possessed by the dye polymer with an unsaturated bond-containing epoxy compound includes glycidyl methacrylate, glycidyl acrylate, Allyl glycidyl ether, propylene Acid-3,4-epoxy-cyclohexylmethyl ester, methacrylic-3,4-epoxy-cyclohexylmethyl ester, etc., especially glycidyl methacrylate and methacrylic acid-3,4-epoxy- Cyclohexyl methyl ester is excellent in crosslinkability and storage stability, and is preferable. As the reaction conditions, known conditions can be used.

(b) The unsaturated bond-containing isocyanate compound in the method of reacting a hydroxyl group or an amine group possessed by the dye polymer with an unsaturated bond-containing isocyanate compound may be exemplified by methacrylic acid-2-isocyanatoethyl group. Ester, 2-isocyanatoethyl acrylate, 1,1-bis (propenyloxymethyl) ethyl isocyanate, etc., 2-isocyanatoethyl methacrylate has good crosslinkability and storage stability Excellent in performance and better. As the reaction conditions, known conditions can be used.

(c) The unsaturated bond-containing carboxylic acid compound in the method for reacting an epoxy compound possessed by the dye polymer with an unsaturated bond-containing carboxylic acid compound is a known one having a (meth) acryloxy group. The carboxylic acid compound can be used without particular limitation, and methacrylic acid and acrylic acid are preferred, and methacrylic acid is particularly excellent in crosslinkability and storage stability. As the reaction conditions, known conditions can be used.

(2) A method of introducing a polymerizable group by copolymerizing a pigment monomer with a polymerizable group-containing compound: (2) A method of introducing a polymerizable group by copolymerizing a pigment monomer and a polymerizable group-containing compound A known method is used without particular limitation, and it is preferred that (d) a method of copolymerizing a pigment monomer capable of radical polymerization with a polymerizable group-containing compound capable of radical polymerization, and (e) enabling A method for copolymerizing a pigmented monomer that is additionally added and a polymerizable group-containing compound that can be further added.

(d) Free radical polymerizable pigment monomer and free radical polymerizable Among the methods for polymerizing a polymerizable group-containing compound to be copolymerized, examples of the polymerizable group-containing compound capable of radical polymerization include allyl-containing compounds (for example, allyl (meth) acrylate, etc.), Epoxy-containing compounds (e.g. glycidyl (meth) acrylate, 3,4-epoxy-cyclohexyl methyl (meth) acrylate, etc.), oxetanyl-containing compounds (e.g. (methyl Group) acrylic acid 3-methyl-3-oxetanyl methyl ester, etc.), methylol group-containing compounds (e.g. N- (hydroxymethyl) acrylamide, etc.), particularly preferably epoxy compounds, oxetan Butane compounds. As the reaction conditions, known conditions can be used.

(e) The polymerizable group-containing compound that can be subjected to the additional addition in the method of copolymerizing the pigmentable monomer that can be subjected to the additional addition and the polymerizable group-containing compound that can be subjected to the addition includes an unsaturated group. Bonded diol compounds (for example, 2,3-dihydroxypropyl (meth) acrylate). As the reaction conditions, known conditions can be used.

The method of introducing a polymerizable group is particularly preferably a method of reacting a carboxylic acid possessed by the dye polymer with an unsaturated bond-containing epoxy compound.

With respect to 1 g of the dye polymer (A), the polymerizable group amount of the dye polymer is preferably 0.1 mmol to 2.0 mmol, more preferably 0.2 mmol to 1.5 mmol, and even more preferably 0.3 mmol to 1.0 mmol.

In addition, the ratio of the repeating unit containing the repeating unit having a polymerizable group to the pigment polymer is, for example, 5 to 50 mol, and more preferably 10 to 20 mol, with respect to 100 mol of all the repeating units. .

The method of introducing a polymerizable group is particularly preferably a method of reacting a carboxylic acid possessed by the dye polymer with an unsaturated bond-containing epoxy compound.

Specific examples of the repeating unit having a polymerizable group are as follows. Among them, this The invention is not limited to these specific examples.

[Chemical 24]

In the specific examples, from the viewpoint of substrate adhesion and surface roughness, pigment monomers having an ethylenically unsaturated bond are preferred, and among these, methacrylfluorenyl, acrylfluorenyl, and styryl are preferred. Or vinyloxy, more preferably methacrylfluorenyl, acrylfluorenyl, and even more preferably methacrylfluorenyl.

<<< Acid group and alkali-soluble group possessed by the pigment polymer (A) >>>

Examples of the acid group that the dye polymer 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, it is preferable that the acid group and / or the alkali-soluble group is preferably contained in the pigment polymer as a repeating unit having an acid group and / or an alkali-soluble group.

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

The acid value of the dye polymer can be calculated, for example, from the average content of acid groups in the dye polymer. In addition, a resin having a desired acid value can be obtained by changing the content of the acid group-containing monomer units constituting the dye polymer.

Examples of the method for introducing an alkali-soluble group into a pigment polymer include a method for introducing an alkali-soluble group into a pigment monomer in advance, and a monomer ((meth) acrylic acid) other than a pigment monomer having an alkali-soluble group. Caprolactone acrylic acid modified product, 2-hydroxyethyl (meth) acrylic acid modified product of succinic anhydride, 2-hydroxyethyl (meth) acrylic acid modified product of phthalic anhydride, (meth) acrylic acid 2- Modified 1,2-cyclohexanedicarboxylic anhydride of hydroxyethyl ester, carboxylic acid-containing monomers such as styrenecarboxylic acid, itaconic acid, maleic acid, norbornenecarboxylic acid, etc. Method of copolymerizing phosphoric acid-containing monomers such as methyl methacrylate, vinylphosphonic acid, and sulfonic acid-containing monomers such as vinylsulfonic acid, 2-acrylamido-2-methylsulfonic acid) To use these two methods.

Relative to 1 g of the pigment polymer, the amount of alkali-soluble groups of the pigment polymer is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and even more preferably 0.5 mmol to 1.0 mmol.

When the dye polymer contains a repeating unit containing a dye monomer and an repeating unit containing an acid group, the ratio of the repeating unit containing an acid group to the repeating unit containing the dye monomer is 100 moles, for example. 5 mol to 70 mol, more preferably 10 mol to 50 mol.

Examples of other functional groups of the dye polymer include lactones, anhydrides, amidines, -COCH ₂ CO-, cyano and other development-promoting groups, long-chain and cyclic alkyl groups, aralkyl groups, aryl groups, and polymer groups. Hydrophilicity-adjusting groups such as an epoxy alkyl group, a hydroxyl group, a maleimidine imide group, and an amine group can be appropriately introduced.

Examples of the method of introduction include a method of introducing into a pigment monomer in advance, and a method of copolymerizing a monomer having the functional group.

Specific examples of the repeating unit having another functional group contained in the dye polymer are shown, but the present invention is not limited thereto.

[Chemical 25]

[Chemical 26]

[Chemical 28]

<<< (A2) form >>>

The form of the dye polymer (A2) is a dye polymer containing a repeating unit having a dye structure and a dye structure having an anion site.

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

Formula (a2) [Chem. 30]

(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 pigment structure having a cationic site and an anionic site)

In the general formula (a2), X ¹ and L ¹ have the same meaning as the general formula (a1-1), and preferred ranges are also the same.

In the general formula (a2), DyeIA is one in which DyeI in the general formula (a1-1) further has an anion site. Examples of the anion site include -SO ^3- and -CO ₂ ^2- .

For specific examples of the form of the dye polymer (A2), reference may be made to A-1, A-3 to A-6 described in paragraph 0069 of Japanese Patent Application Laid-Open No. 2012-032754, and the contents are incorporated into this specification. .

<<< Form of (A3) >>>

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

The monomer having a pigment structure has the same meaning as the monomer containing a partial structure derived from an xanthracene compound represented by the general formula (J).

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

Formula (a3) [Chem. 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 has the same meaning as the general formula (a1-1), and the preferred ranges are also the same.

In the general formula (a3), when L ² represents a divalent linking group, an alkylene group having a carbon number of 1 to 20 (preferably 1 to 10), and a carbon number of 6 to 20 (preferably 6) ~ 10) arylene, heterocyclic group with 4 to 20 carbons (preferably 5 to 10), alkylsulfonyl group with 1 to 20 carbons (preferably 1 to 10), 6 to 6 carbons 20 (preferably 6 to 10) arylsulfonyl, alkyl carbonyl having 1 to 20 (preferably 1 to 10), aryl 6 to 20 (preferably 6 to 11) aryl Carbonyl group, alkylamino group having 1 to 20 carbon atoms (preferably 1 to 10), arylamino group having 6 to 20 carbon atoms (preferably 6 to 10), and 1 to 20 carbon atoms (preferably 1) ~ 10) alkylcarbonyloxy, arylcarbonyloxy having 6 to 20 carbon atoms (preferably 6 to 11), and the like. These divalent linking groups are preferably substituted with an electron withdrawing group. Examples of the electron withdrawing group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a nitro group, a cyano group, and a halogenated alkyl group (for example, Trifluoromethyl), halogenated aryl.

In the case where Z in the general formula (1) described later is a low-nucleophilic anion structure represented by the general formula (2-1), L ^{2 is} preferably a carbon atom having 1 to 10 carbon atoms substituted with a fluorine atom. Alkyl (fluorinated alkylene).

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

General formula (2-1) *-Y ¹ -A ¹

(In the general formula (2-1), * represents the general formula (L bonded portion a3) in ^2, Y ¹ represents a fluorinated alkylene group, A ¹ represents SO ₃ ^-)

(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)

Hereinafter, specific examples of the repeating unit represented by the general formula (a3) used in the present invention are shown, but the present invention is not limited thereto. The specific example shows a state where the anion site is not dissociated, but the state where the anion site is dissociated is of course within the scope of the present invention.

[Chemical 33]

<<< (A4) form >>>

The form of the dye polymer (A4) is a dye polymer having other cation and anion sites. For example, it is a pigment polymer having a pigment structure monomer and a repeating unit having a cationic site, and a pigment structure-containing monomer containing a corresponding anion site.

Refer to Japanese Patent Laid-Open for a repeating unit having a cationic site The descriptions of paragraphs 0018 to 0061 in the 2011-242752 publication are incorporated into this specification.

Examples of a pigment structure-containing monomer containing a corresponding anion site include Color Index (C.I.) Acid Red 289.

For a specific example of the dye polymer (A4), reference may be made to the description in paragraph 0165 of Japanese Patent Application Laid-Open No. 2011-242752, and the contents are incorporated into this specification.

The pigment polymer preferably has a maximum absorption wavelength of 420 nm to 700 nm, and more preferably 450 nm to 650 nm.

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

In the present invention, when the total value of the repeating units is set to 100 mol% (mole percentage), the repeating unit containing the structure derived from the pigment is preferably 10 mol% to 100 mol% in the pigment polymer, and more preferably 50mol% ~ 100mol%, particularly preferably 60mol% ~ 100mol%.

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

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

In addition, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the pigment polymer [(Mw) / (Mn)] is preferably 1.0 to 3.0, more preferably 1.6 to 2.5, and even more preferably 1.6 to 2.5. 2.0.

The glass transition temperature (Tg) of the pigment polymer is preferably 50 ° C or higher, It is more preferably 100 ° C or higher. The 5% weight reduction temperature obtained by thermogravimetric analysis (TGA measurement) is preferably 120 ° C or higher, more preferably 150 ° C or higher, and even more preferably 200 ° C or higher.

The light absorption coefficient per unit weight of the dye polymer (hereinafter referred to as ε '. Ε' = ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, more preferably 60 or more, and even more preferably It is 100 or more. With this range, when a color filter is produced by applying the coloring composition of the present invention, a color filter with good color reproducibility can be produced.

From the viewpoint of tinting power, the molar absorption coefficient of the pigment polymer is preferably as high as possible.

From the viewpoint of color shift, the reducing viscosity of the pigment polymer is preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and even more preferably 6.0 to 7.0. The reduced viscosity can be measured using, for example, an Ubbelohde viscometer.

The pigment polymer is preferably 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, methyl 3-methoxypropionate, etc.), ethers (Such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclic (Hexanone, 2-heptanone, 3-heptanone, etc.) and aromatic hydrocarbons (such as toluene, xylene, etc.) are preferably as follows: relative to these solvents, it is preferable to dissolve 1% by mass or more, 50% Mass% or less, more preferably 5 mass% or more and 40 mass% or less, still more preferably 10 mass% or more and 30 mass% or less. By being within this range, the work of the present invention will be When the color composition is used in the production of a color filter, etc., a better coating surface shape can be achieved, or the concentration reduction caused by dissolution after coating with other colors can be reduced.

The coloring composition of the present invention may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount is preferably equivalent to the content described later.

The content of the pigment polymer (A) in the coloring composition of the present invention is preferably set in consideration of the content ratio with the pigment described later.

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

The coloring composition of this invention may contain well-known dyes other than the said dye polymer.

For example, refer to Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, and Japanese Patent Registration 2592207 No., U.S. Patent No. 4885501, U.S. Patent No. 5667920, U.S. Patent No. 505950, U.S. Patent No. 5667920, JP-A No. 5-333207, JP-A No. 6-35183, JP-A No. 6-35183 6-51115, Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. 2010-250291, Japanese Patent Laid-Open No. 2011-95732, Japanese Patent Laid-Open No. 2012-13945, Japanese Patent Laid-Open No. 2012-46708, Japanese Patent Laid-Open No. 2012-46712, Japanese Patent Laid-Open No. 2012-181502, Japanese Patent Laid-Open No. 2012-208494, Japanese Patent Laid-Open No. 2013-28764 Japanese Patent Application Publication No. 2013-29760, incorporates these contents into the specification of the present application. Chemical structure can be used: pyrazole azo-based, pyrrole methylene-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, benzylidene-based, oxazolyl-based, pyrazolotriazole-azo-based , Pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazoleimine-based dyes and the like.

<< (B) Solvent >>

The coloring composition of the present invention contains a solvent.

The solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the colored composition, and it is particularly preferred to consider the solubility, coatability, and safety of ultraviolet absorbers, alkali-soluble resins, or dispersants. select.

As the solvent, as the esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate are mentioned as the esters. , Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl ethoxylate, butyl oxyacetate (e.g. methoxyacetic acid) Methyl ester, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionates (e.g. 3-oxy Methyl propionate, ethyl 3-oxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), alkyl 2-oxypropionates (e.g. methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g. (Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) ), Methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropanoate (e.g. 2-methoxy-2- Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate , Methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl ether Base cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether ethyl Esters, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, cyclopentanone, etc .; Examples of the aromatic hydrocarbons include toluene and xylene.

Among these solvents, a solvent having a molecular weight in a range of 80 to 135 or a boiling point in a range of 120 ° C to 160 ° C is preferred from the viewpoint of drying after coating. Examples of the solvent equivalent to these solvents include n-butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, and cyclopentanone.

In addition to the viewpoints mentioned above, these organic solvents can further improve the storage stability by using solvents having excellent solubility of xanthracene dye in the solvent, such as cyclohexanone, cyclopentanone, and propylene glycol monomethyl ether. Sex. As a specific example, by using propylene glycol monomethyl ether acetate as a main solvent and containing 10% or more of one or more solvents selected from cyclohexanone, cyclopentanone, and propylene glycol monomethyl ether, coating properties can be improved at the same time. With placement stability.

From the viewpoint of coatability, the content of the solvent in the coloring composition is preferably set such that the total solid content concentration of the composition becomes 5 to 80% by mass, and more preferably 5 to 60% by mass. , Especially preferably 10% to 50% by mass.

The composition of the present invention may contain only one solvent or two or more solvents. When it contains two or more types, it is preferable that the total amount is the said range.

<Hardening compound>

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

As the curable compound, a known polymerizable compound that can be crosslinked by radicals, acids, and heat can be used, and examples thereof include an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane), and a hydroxyl group. Polymerizable compounds such as methyl. From the viewpoint of sensitivity, the polymerizable compound is preferably selected from compounds having at least one terminal ethylenic unsaturated bond, preferably two or more.

Among these, a polyfunctional polymerizable compound is preferred, a polyfunctional polymerizable compound having 4 or more functions is more preferred, a 5-functional or more function is more preferred, and a 6-functional or more function is more preferred.

Particularly preferred is a polyfunctional monomer (preferably 4 or more, more preferably 6 or more) and modified by an alkylene oxide.

Such compound groups are widely known in the industrial field of the present invention, and these compounds can be used in the present invention without any particular limitation. These compounds may be, for example, any of the following chemical forms: monomers, prepolymers, such as dimers, trimers, and oligomers, or mixtures of these, and such polymers. The polymerizable compound of the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and its prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylic acid, maleic acid, etc.) or their esters, The amines and these polymers are preferably esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and unsaturated carboxylic acids and an aliphatic polyamine Amines of compounds and polymers thereof. In addition, it is also preferable to use the following reactants: addition of unsaturated carboxylic acid esters or amidoamines having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy Reactants, or dehydration condensation reactants with monofunctional or polyfunctional carboxylic acids, and the like. In addition, the following reactants are also preferred: the addition of unsaturated carboxylic acid esters or amidines having an electrophilic substituent such as an isocyanate group or an epoxy group, and the addition of monofunctional or polyfunctional alcohols, amines, and thiols. Substitute reactants of unsaturated carboxylic acid esters or amidoamines having a detachable substituent such as a halogen group or tosylsulfonyloxy group and monofunctional or polyfunctional alcohols, amines, or thiols. In addition, as another example, a group of compounds in which the unsaturated carboxylic acid is replaced with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like may be used.

As such specific compounds, the compounds described in paragraphs 0095 to 0108 of Japanese Patent Laid-Open No. 2009-288705 can be preferably used in the present invention.

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one vinyl group capable of addition polymerization and having a boiling point of 100 ° C. or higher under normal pressure. Examples thereof include: monofunctional acrylates or methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; poly Ethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (methyl) Base) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylic acid Ester, trimethylolpropane tris (propenyloxypropyl) ether, tris (propenyloxyethyl) isocyanurate, addition to polyfunctional alcohols such as glycerol or trimethylolethane Ethylene oxide or propylene oxide esterified with (meth) acrylic acid, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193 The (meth) acrylic acid urethanes described in the publication are described in Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191, and Japanese Patent Laid-Open No. 52-30490. Ester acrylates are polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.

Polyfunctional (meth) acrylates and the like are also mentioned. The polyfunctional (meth) acrylate is a compound having a cyclic ether group and an ethylenically unsaturated group, such as glycidyl (meth) acrylate, and a polyfunctional group. Carboxylic acid reaction.

In addition, other preferable polymerizable compounds can also be used: Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, and the like having a fluorene ring and bifunctionality. The above-mentioned ethylenically unsaturated compound is Cardo resin.

In addition, a compound having a boiling point of 100 ° C. or more under normal pressure and having at least one ethylenically unsaturated group capable of addition polymerization is also preferably paragraph number [0254] of Japanese Patent Laid-Open No. 2008-292970 The compound described in paragraph number [0257].

In addition to the above, a radically polymerizable monomer represented by the following general formula (MO-1) to general formula (MO-5) can be preferably used. Moreover, in the formula, T is In the case of oxyalkylene, the terminal on the carbon atom side is bonded to R.

[Chemical 35]

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

In each polymerizable compound represented by the general formula (MO-1) to the general formula (MO-5), at least one of a plurality of Rs represents -OC (= O) CH = CH ₂ or -OC ( = O) C (CH ₃ ) = CH ₂ represents a group.

As specific examples of the polymerizable compound represented by the general formula (MO-1) to the general formula (MO-5), paragraphs 0248 to 0251 of Japanese Patent Laid-Open No. 2007-269779 may be described. The compounds are preferably used in the present invention.

In addition, the following compounds can also be used as polymerizable compounds: as described in Japanese Patent Application Laid-Open No. 10-62986 as a general formula (1) and a general formula (2), which are described on polyfunctional alcohols together with specific examples thereof. A compound obtained by addition of ethylene oxide or propylene oxide and (meth) acrylic acid esterification.

Among them, the polymerizable compound is preferably dipentaerythritol triacrylate (a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (a commercially available product is Kaya Lay (KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (Meth) acrylic acid ester (commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and (meth) acrylfluorenyl groups are separated by ethylene glycol residues and propylene glycol residues Base structure. These types of oligomers can also be used.

The polymerizable compound may be a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphate group. As long as the ethylenic compound has an unreacted carboxyl group as described above as a mixture, it can be used as it is, and if necessary, a non-aromatic carboxylic anhydride can be reacted with a hydroxyl group of the ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexa Hydrophthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and it is preferred that a non-aromatic carboxylic acid anhydride reacts with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group. The polyfunctional monomer is particularly preferably one in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol. Commercial products include, for example, M-510, M-520, which are polyacid-modified acrylic oligomers manufactured by Toa Synthesis Co., Ltd., and the like.

These monomers may be used singly, but it is difficult to use a single compound in terms of production, and therefore, two or more kinds may be used in combination. In addition, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination. body.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing and dissolving properties are lowered. If the acid value of the polyfunctional monomer is too high, manufacturing or handling becomes difficult, the photopolymerization performance decreases, and hardenability such as the surface smoothness of the pixel is deteriorated. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferable to use the acid groups of the entire polyfunctional monomer in the same place. Adjust in the manner mentioned above.

A polymerizable compound containing a polyfunctional monomer having a caprolactone structure is also preferred.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule. For example, ε-caprolactone-modified polyfunctional (meth) acrylate can be mentioned. Caprolactone is modified by multifunctional (meth) acrylate by trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, Polyols such as pentaerythritol, tripentaerythritol, glycerol, diglycerin, and trimethylolmelamine are obtained by esterification with (meth) acrylic acid and ε-caprolactone. Among these, a polyfunctional monomer having a caprolactone structure represented by the following general formula (Z-1) is preferred.

[Chemical 36]

In the general formula (Z-1), all six Rs are groups represented by the following general formula (Z-2), or one to five of the six Rs are the following general formula (Z-2) And the rest are groups represented by the following general formula (Z-3).

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.

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 as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., for example, DPCA-20 (the above formula (1) ~ In formula (3), m = 1, the number of groups represented by formula (2) = 2, and compounds in which all of R ¹ are hydrogen atoms), DPCA-30 (in formulas (1) to (3) m = 1, the number of groups represented by the formula (2) = 3, compounds in which all of R ¹ is a hydrogen atom), DPCA-60 (m = 1 in the formula (1) to formula (3), formula (2) The number of groups represented by the compound = 6, all compounds where R ¹ is a hydrogen atom), DPCA-120 (where m = 2 in the formula (1) to formula (3), and formula (2) Number of groups = 6, compounds in which all of R ¹ is a hydrogen atom) and the like.

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

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

In the general formula (Z-4) and the general formula (Z-5), E each independently represents-((CH ₂ ) yCH ₂ O)-or-((CH ₂ ) yCH (CH ₃ ) O)- , Y each independently represents an integer of 0 to 10, and X each independently represents an acrylfluorenyl group, a methacrylfluorenyl group, a hydrogen atom, or a carboxyl group.

In the general formula (Z-4), the total value of acrylfluorenyl and methacrylfluorenyl is 3 or 4, m represents an integer of 0 to 10, and the total value of each m is 0 to 40. Integer. However, when the total value of each m is 0, any one of X is a carboxyl group.

In the general formula (ii), the total value of the propylene acryl and methacryl groups is five or six, n each independently represents an integer of 0 to 10, and the total value of each n is an integer of 0 to 60 . However, when the total value 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, and more preferably an integer of 0 to 4. In addition, the total value of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.

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

In addition, the total value of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.

Moreover,-((CH ₂ ) yCH ₂ O)-or-((CH ₂ ) yCH (CH ₃ ) O)-in the general formula (Z-4) or (Z-5) is preferably an oxygen atom. The side end is bonded to the morphology of X.

The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more kinds. It is particularly preferable that all six X's in the general formula (ii) are acrylfluorenyl groups.

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by the following steps, which are conventionally known steps: the reaction of ethylene oxide or propylene oxide by a ring-opening addition reaction A step of bonding a ring-opening skeleton to pentaerythritol or dipentaerythritol; and a step of introducing, for example, a (meth) acrylfluorenyl group by reacting (meth) acrylfluorene chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or the general formula (ii).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.

Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplified compounds (a) to (f)"). Among them, exemplary compounds (a) and exemplified compounds are preferred. Compound (b), Exemplified compound (e), Exemplified compound (f).

[Chemical 40]

[Chemical 41]

Examples of commercially available products of the polymerizable compound represented by the general formula (Z-4) and the general formula (Z-5) include a tetrafunctional acrylic acid having four ethoxyl chains manufactured by Sartomer Corporation. Ester SR-494, hexafunctional acrylate DPCA-60 with 6 pentyloxy chains, trifunctional acrylate TPA-330 with 3 butyloxy groups, etc., manufactured by Nippon Kayaku Co., Ltd.

In addition, the polymerizable compound is also preferably in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Documentary acrylic urethanes, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japan Japanese Unexamined Patent Publication No. 62-39418 discloses urethane compounds having an ethylene oxide-based skeleton. Furthermore, by using JP-A-63-277653, JP-A-63-260909, and JP-A-105238, it has an amine structure or a thioether structure in the molecule. As the polymerizable compound, the addition polymerizable compounds are obtainable as a curable composition having a very excellent photosensitivity.

Examples of commercially available polymerizable compounds include urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Sanyo Kokusei Pulp & Paper Co., Ltd.), and "UA-7200" (Shinakamura Chemical (Manufactured by the company), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha).

Regarding cyclic ethers (epoxy, oxetane), for example, as those having epoxy groups, the bisphenol A type epoxy resin is JER-827, JER-828, JER-834, JER-1001, JER-1002 , JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (the above are made by Japan Epoxy Resin (stock)), EPICLON 860, EPICLON 1050, Ai Epiclon 1051, Epiclon 1055 (the above are manufactured by DIC), etc. The bisphenol F-type epoxy resin is JER-806, JER-807, JER-4004, JER -4005, JER-4007, JER-4010 (above are manufactured by Japan Epoxy Resin), EPICLON 830, EPICLON 835 (above are manufactured by DIC) ), LCE-21, RE-602S (the above are manufactured by Nippon Kayaku Co., Ltd.), etc., the phenol novolac epoxy resin is JER-152, JER-154, JER-157S70, JER-157S65 (the above are manufactured by Japan Epoxy Resin (stock)), EPICLON N-740, EPICLON N-770, EPICLON N-775 ( The above are manufactured by DIC, etc. Examples of the cresol novolac epoxy resin include EPICLON N-660, EPICLON N-665, and EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (The above is DIC ) (Manufactured by), EOCN-1020 (the above are manufactured by Nippon Kayaku Co., Ltd.), and aliphatic epoxy resins can be exemplified by ADEKA RESIN EP-4080S, ADEKA RESIN EP -4085S, ADEKA RESIN EP-4088S (the above is made by ADEKA), Celloxide 2021P, Celloxide 2081, Celloxi Celloxide 2083, Celloxide 2085, EHPE-3150 (1,2,2-bis (hydroxymethyl) -1-butanol, 1,2-epoxy-4- (2-oxane (Propyl) cyclohexane adduct), EPOLEAD PB 3600, EPOLEAD PB 4700 (above is Cellulose) (Daicel Chemical Industry Co., Ltd.), Denacol EX-211L, Denacol EX-212L, Denacol EX-214L, Denacol ) EX-216L, Denacol EX-321L, Denacol EX-850L (the above are made by Nagase Chemtex), ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN RESIN) EP-4011S (the above are manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (the above are the products of (ADEKA) (manufactured by Japan), JER-1031S (manufactured by Japan Epoxy Co., Ltd.), etc. Such a polymerizable compound is suitable when a pattern is formed by a dry etching method.

These polymerizable compounds can be arbitrarily set according to the final performance design of the coloring composition, such as the structure, the method of use alone or in combination, and the amount of use. For example, from the viewpoint of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferred, and in many cases, a structure having more than two functions is preferred. In addition, from the viewpoint of improving the strength of the cured film formed of the coloring composition, it is preferable to use trifunctional or higher functionalities. Furthermore, by using a combination of different functional groups and different polymerizable groups (for example, acrylate, methacrylic acid) Ester, styrene-based compound, vinyl ether-based compound) to adjust both sensitivity and intensity. Furthermore, it is preferable to use a polymerizable compound having a trifunctional or more functionality and different ethylene oxide chain lengths in that the developability of the coloring composition can be adjusted and excellent pattern forming ability can be obtained.

In addition, in terms of compatibility and dispersibility with other components contained in the coloring composition (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, etc.), the selection and use of a polymerizable compound is also important. For example, compatibility may be improved by using a low-purity compound or a combination of two or more. In addition, from the viewpoint of improving the adhesion to a hard surface such as a support, a specific structure may be selected.

With respect to the total solid content in the composition, the hardness in the composition of the present invention is The content of the chemical compound is preferably 0.1% to 90% by mass, more preferably 1.0% to 60% by mass, and even more preferably 2.0% to 40% by mass.

The composition of the present invention may contain only one type of curable compound, or may contain two or more types. When it contains two or more types, it is preferable that the total amount is the said range.

<Pigment>

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 organic pigments are preferably used. The pigment is preferably high in transmittance.

Examples of the inorganic pigment include metal compounds represented by metal oxides and metal salts, and specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. The metal composite oxides are black pigments such as carbon black and titanium black.

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

The pigments which can be preferably used in the present invention include the following pigments. However, the present invention is not limited to these pigments.

CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Orange 36, CI Pigment Orange 71, CI Pigment Red 122, CI Pigment Red 150, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, CI Pigment Blue 15: 1. CI Pigment Blue 15: 3, CI Pigment Blue 15: 6, CI Pigment Blue 16, C.I.Pigment Blue 22, C.I.Pigment Blue 60, C.I.Pigment Blue 66, C.I.Pigment Green 7, C.I.Pigment Green 36, C.I.Pigment Green 37, C.I.Pigment Green 58; C.I.Pigment Black 1

These organic pigments can be used singly or in combination in order to adjust the spectrum or improve the color purity. A specific example of the combination is shown below. For example, as the red pigment, an anthraquinone-based pigment, a fluorene-based pigment, and a diketopyrrolopyrrole-based pigment can be used alone, or at least one of these pigments can be used with a bisazo-based yellow pigment, an isoindoline-based yellow pigment, or quinphthalein Mixtures of ketone-based yellow pigments and fluorene-based red pigments. For example, anthraquinone-based pigments include CI Pigment Red 177, fluorene-based pigments include CI Pigment Red 155, CI Pigment Red 224, and diketopyrrolopyrrole-based pigments include CI Pigment Red 254. In terms of color decomposition properties , Preferably mixed with CI Pigment Yellow 139. In addition, the quality of the red pigment and the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it is difficult to suppress the light transmittance from 400nm to 500nm, and if it is 100: 51 or more, the main wavelength may be shifted to a short wavelength, and the color resolution ability may not be improved. In particular, the most suitable mass ratio is in the range of 100: 10 to 100: 30. In addition, in the case of a combination of red pigments, adjustment can be made according to the required spectrometry.

In addition, as the green pigment, a halogenated phthalocyanine-based pigment may be used alone, or a mixture thereof with a bisazo-based yellow pigment, a quinophthalone-based yellow pigment, a methylimine-based yellow pigment, or an isoindoline-based yellow pigment. For example, such examples are preferably CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Yellow 185 mix. The quality of the green pigment and the yellow pigment is better: 100: 5 ~ 100: 150. The mass ratio is particularly preferably in a range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture thereof with a dioxazine-based purple pigment may be used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I. Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is preferably 100: 0 to 100: 100, and more preferably 100: 10 or less.

The black matrix pigment can be used alone or in combination with carbon, titanium black, iron oxide, and titanium oxide, and a combination of carbon and titanium black is preferred. In addition, the comparatively good quality of carbon and titanium black is in the range of 100: 0 to 100: 60.

The coloring composition of the present invention is preferably a pigment other than black, and is suitable for a blue pigment.

The primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast when used for a color filter, and more preferably from the viewpoint of dispersion stability. 5nm or more. The primary particle size of the pigment is preferably 5 nm to 75 nm, more preferably 5 nm to 55 nm, and even more preferably 5 nm 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 the group consisting of anthraquinone pigment, diketopyrrolopyrrole pigment, phthalocyanine pigment, quinophthalone pigment, isoindoline pigment, methylimine pigment, and dioxazine pigment. Especially preferred are CI Pigment Red 177 (Anthraquinone Pigment), CI Pigment Red 254 (Diketopyrrolopyrrole Pigment), CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15: 6 (phthalate Cyanine pigment), CI pigment yellow 138 (quinophthalone pigment), CI pigment yellow 139, CI pigment yellow 185 (isoindoline pigment), CI Pigment Yellow 150 (methimine pigment), C.I. Pigment Violet 23 (dioxazine pigment).

Particularly, the pigment is preferably a phthalocyanine pigment.

In the case where a phthalocyanine pigment is used as the pigment, the quality of the phthalocyanine pigment and the pigment polymer is better: phthalocyanine pigment: pigment polymer = 100: 10 ~ 100: 100, more preferably 100: 20 ~ 100: 80.

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

Regarding the content in the case where a phthalocyanine pigment is used as the pigment, the content is preferably from 10% by mass to 70% by mass, and more preferably from 20% by mass to 60% by mass, with respect to all components excluding the solvent contained in the coloring composition. %, More preferably 25% by mass to 50% by mass.

The composition of the present invention may contain only one kind of pigment, or may contain two or more kinds. When it contains two or more types, it is preferable that the total amount is the said range.

<Photopolymerization initiator>

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

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having a sensitivity in the ultraviolet range to visible light are preferred. In addition, it may be an active agent that generates some active radicals by interacting with a photo-excited sensitizer, or an initiator that initiates cationic polymerization depending on the type of monomer.

In addition, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in 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 those having an oxadiazole skeleton), fluorenylphosphine compounds such as a fluorenylphosphine oxide, hexaarylbiimidazole, and oxime derivatives Other oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like are preferred, and oxime compounds are preferred.

In addition, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzophenone dimethyl ketal compound, an α-hydroxyketone compound, an α-amino ketone compound, and a fluorenylphosphine. Compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene -Compounds in the group consisting of iron complexes and their salts, halogenated methyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

Further preferred are trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, triarylimidazole compounds, benzimidazole compounds, and oniums. Compounds, benzophenone compounds, acetophenone compounds, particularly preferably selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole compounds, benzophenone compounds, and triaryl groups At least one compound in the group consisting of an imidazole compound and a benzimidazole compound. The triarylimidazole compound may be a mixture with benzimidazole.

Specific examples of the trihalomethyltriazine compound include the following compounds. In addition, Ph is phenyl.

Examples of the triarylimidazole compound and the benzimidazole compound include the following compounds.

As the trihalomethyltriazine compound, a commercially available product may be used, and for example, TAZ-107 (manufactured by Bichem Corporation) can be used.

In particular, when the colored composition of the present invention is used to produce a color filter included in a solid-state imaging element, it is necessary to form a fine pattern in a sharp shape. Therefore, it is important that it is hardenable and is applied to the unexposed portion. Development was carried out without residue. From such a viewpoint, the polymerization initiator is particularly preferably an oxime compound. Especially In the case where a fine pattern is formed in a solid-state imaging device, stepwise exposure is used for curing exposure. However, the exposure machine may be damaged due to halogen, and the addition amount of the polymerization initiator must be kept low. Considering these points, it is particularly preferable to use an oxime compound as the (D) photopolymerization initiator when forming a fine pattern like a solid-state imaging element.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include compounds described in "Bull.Chem.Soc.Japan" (42, 2924 (1969)) by Wakabayashi et al., And British Patent No. 1384492 The compound described in the No. specification, the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in the German Patent No. 3370024, FC Schaefer, and others, "Journal of Organic Chemistry (J. Org. Chem. .) "(29, 1527 (1964)), the compound described in Japanese Patent Laid-Open No. 62-58241, the compound described in Japanese Patent Laid-Open No. 5-281728, and Japanese Patent Laid-Open No. 5-34920 The compounds described in the gazette, the compounds described in the specification of U.S. Patent No. 4,212,976, and particularly the compounds described in paragraph number 0075 of Japanese Patent Laid-Open No. 2013-077009.

Examples of the photopolymerization initiator other than the above include acridine derivatives. Specific examples include compounds described in paragraph number 0076 of Japanese Patent Laid-Open No. 2013-077009, and these contents are incorporated into the specification of the present application.

Examples of the ketone compound include compounds described in paragraph number 0077 of Japanese Patent Application Laid-Open No. 2013-077009, and these contents are incorporated in the description of the present application.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

Hydroxyacetophenone-based initiators can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IGACURE-2959 (IRGACURE) -127 (trade name: all manufactured by BASF). Aminoacetophenone-based initiators can be used: IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: BASF), which are commercially available products. (BASF). As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 can be used in which the absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm. As the fluorenylphosphine-based initiator, commercially available products, IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF) can also be used.

The photopolymerization initiator is more preferably an oxime compound. Specific examples of the oxime compound include compounds described in Japanese Patent Laid-Open No. 2001-233842, compounds described in Japanese Patent Laid-Open No. 2000-80068, and compounds described in Japanese Patent Laid-Open No. 2006-342166.

Examples of the oxime compound such as an oxime derivative which can be preferably used as the photopolymerization initiator of the present invention include 3-benzyloxyiminobutane-2-one and 3-acetamidoxyimine Butane-2-one, 3-propanyloxyiminobutane-2-one, 2-acetamidooxyimine Pentane-3-one, 2-ethoxyloxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3 -(4-toluenesulfonyloxy) iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and the like.

Examples of oxime compounds are: "Journal of the Chemical Society (JCS) Perkin II" (1979) pp. 1653-1660, "Journal of the Chemical Society, JCS) Perkin II (1979) pp. 156-162, `` Journal of Photopolymer Science and Technology '' (1995) pp. 202-232, Japanese patent Compounds described in JP-A-2000-66385, compounds described in JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166.

Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be preferably used.

In addition, the following compounds may also be used as oxime compounds other than those described in the above: Compounds described in Japanese Patent Publication No. 2009-519904, in which the oxime is bonded to the N-position of carbazole, and heterosubstitution is introduced into the benzophenone site Compounds described in U.S. Patent No. 7,626,957, compounds disclosed in Japanese Patent Laid-Open No. 2010-15025 in which a nitro group is introduced into a pigment portion, and U.S. Patent Publication No. 2009-292039, and International Publication No. 2009-131189 The ketoxime compound described in the publication contains U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule. The compounds described in the publication, and the compounds described in Japanese Patent Application Laid-Open No. 2009-221114, which have the maximum absorption at 405 nm and have good sensitivity to a g-ray light source.

The cyclic oxime compound described in Japanese Patent Application Laid-Open No. 2007-231000 and Japanese Patent Application Laid-Open No. 2007-322744 is further preferably used. Among the cyclic oxime compounds, in particular, from the viewpoint of having high light absorption and high sensitivity, the condensed rings described in Japanese Patent Laid-Open No. 2010-32985 and Japanese Patent Laid-Open No. 2010-185072 are preferred. A cyclic oxime compound on a carbazole pigment.

In addition, the compound described in Japanese Patent Application Laid-Open No. 2009-242469 having an unsaturated bond at a specific site of the oxime compound also regenerates active radicals by polymerizing inactive radicals, thereby achieving high sensitivity and making it easier to compare Best to use.

Particularly preferred examples include an oxime compound having a specific substituent disclosed in Japanese Patent Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group disclosed in Japanese Patent Laid-Open No. 2009-191061.

Specifically, the oxime compound as a photopolymerization initiator is preferably a compound represented by the following general formula (OX-1). Furthermore, the oxime compound whose N-O bond of the oxime is the (E) form, the oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form may be used.

[Chemical 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-metal atomic group.

Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group, and the like. These groups may have one or more substituents. In addition, the substituent may be further substituted with another substituent.

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

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. For details, refer to paragraph 0025 of Japanese Patent Application Laid-Open No. 2009-191061, and the content is incorporated into this specification.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms. For details, refer to paragraph 0026 of Japanese Patent Application Laid-Open No. 2009-191061, and the content is incorporated into this specification.

The fluorenyl group is preferably a fluorenyl group having a carbon number of 2 to 20. For details, refer to paragraph 0033 of Japanese Patent Laid-Open No. 2009-191061, and the content is incorporated into this specification.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. For details, refer to paragraph 0034 of Japanese Patent Laid-Open No. 2009-191061, and incorporate the content thereof. To this manual.

The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 6 to 30 carbon atoms, and the content thereof can be incorporated into this specification by referring to paragraph 0035 of Japanese Patent Laid-Open No. 2009-191061.

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.

For details, reference can be made to paragraph 0037 of Japanese Patent Laid-Open No. 2009-191061, and the contents are incorporated into this specification.

The alkylthiocarbonyl group is specifically preferably an alkylthiocarbonyl group having 1 to 20 carbon atoms, and the content thereof can be incorporated into this specification by referring to paragraph 0038 of Japanese Patent Laid-Open No. 2009-191061.

The arylthiocarbonyl group is specifically preferably an arylthiocarbonyl group having 6 to 30 carbon atoms, and the content thereof can be incorporated into this specification by referring to paragraph 0039 of Japanese Patent Laid-Open No. 2009-191061.

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. Examples of the substituent include the substituents described above. In addition, the substituents described above may be further substituted with other substituents.

Among them, it is particularly preferable to refer to paragraph 0044 of Japanese Patent Laid-Open No. 2009-191061, and incorporate the contents into this specification.

Examples of the divalent organic group represented by A in the formula (OX-1) include an alkylene group, a cycloalkylene group, and an alkynyl group having 1 to 12 carbon atoms. In addition, these groups may also have a More than one substituent. Examples of the substituent include the substituents described above. In addition, the substituents described above may be further substituted with other substituents.

Among these, in terms of improving sensitivity and suppressing coloration caused by heating over time, A in the formula (OX-1) is preferably an unsubstituted alkylene group or an alkyl group (for example, methyl, ethyl, etc.). , Tertiary butyl, dodecyl), alkylene substituted with alkenyl (e.g. vinyl, allyl), alkylene substituted with aryl (e.g. phenyl, p-tolyl, xylyl) , Cumenyl, naphthyl, anthracenyl, phenanthryl, styryl).

In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may further have a substituent. Examples of the substituent include the same groups as the substituents introduced into the substituted aryl group listed above as specific examples of the aryl group which may have a substituent.

Among these, a substituted or unsubstituted phenyl group is preferred in terms of improving sensitivity and suppressing coloration caused by heating over time.

In formula (OX-1), for a preferred structure of "SAr" formed by Ar and S adjacent thereto in the formula (OX-1), refer to paragraph 0049 of Japanese Patent Laid-Open No. 2009-191061. The description is incorporated into this specification.

The oxime compound can refer to the description in paragraph 0050 to paragraph 0106 of Japanese Patent Laid-Open No. 2009-191061, and the contents are incorporated into this specification.

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

From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000.

A known method can be used for the compound's Mohr absorption coefficient. Specifically, for example, it is preferable to use a UV-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian). )), Using 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 0.1% to 50% by mass, and more preferably 0.5% with respect to the total solid content of the coloring composition. Mass% to 30% by mass, and further preferably 1% to 20% by mass. Within this range, better sensitivity and pattern formation properties can be obtained.

The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When it contains two or more types, it is preferable that the total amount is the said range.

<Pigment Dispersant>

When the coloring composition of this invention contains a pigment, a pigment dispersing agent may be used together as needed.

Examples of the pigment dispersant usable in the present invention include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, Modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers, formalin naphthalenesulfonic acid], and polyoxyethylene alkyl phosphates, polyoxyethylene Surfactants and pigment derivatives such as amines and alkanolamines.

Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structure.

Examples of the terminally modified polymer having an anchor portion on the surface of the pigment include, for example, Japanese Patent Application Laid-Open No. 3-112992 and Japanese Patent Publication No. 2003-533455. Macromolecules, polymers described in Japanese Patent Laid-Open No. 2002-273191 and the like having a sulfonic acid group at the terminal, and Japanese Patent Application Laid-Open No. 9-77994 and the like having a partial skeleton or heterocyclic ring having an organic dye Molecules, etc. In addition, Japanese Patent Application Laid-Open No. 2007-277514 describes a polymer in which two or more fixing sites (acid group, basic group, partial skeleton or heterocyclic ring of an organic dye, etc.) on the surface of a pigment are introduced into a polymer end. It is also excellent in dispersion stability.

Examples of the graft polymer having a fixed portion on the pigment surface include polyester dispersants. Specific examples include Japanese Patent Laid-Open No. 54-37082, Japanese Patent Laid-Open No. 8-507960, and Japan. Reaction product of poly (lower alkyleneimine) and polyester described in Japanese Patent Laid-Open No. 2009-258668 and the like, and reaction product of polyallylamine and polyester described in Japanese Patent Laid-Open No. 9-169821 and the like , Japanese Patent Laid-Open No. 10-339949, Japanese Patent Laid-Open No. 2004-37986, International Publication Manual WO2010 / 110491, and the copolymer of a macromonomer and a nitrogen atom monomer, Japanese Patent Laid-Open No. 2003-238837 Grafting polymers with partial skeletons or heterocyclic rings of organic pigments described in Japanese Patent Application Publication No. 2008-9426, Japanese Patent Application Publication No. 2008-81732, and the like, Japanese Patent Application Publication No. 2010-106268 Co-existence of macromonomers and acid group-containing monomers described in bulletins and the like Polymer and so on. In particular, from the viewpoints of dispersibility, dispersion stability, and developability of a coloring composition using the pigment dispersion, it is particularly preferred to have basic properties described in Japanese Patent Laid-Open No. 2009-203462. -Based and acidic-based amphoteric dispersion resin.

The macromonomer used in the production of a graft polymer having a fixed portion on a pigment surface by radical polymerization may be a known macromonomer, and examples include the macromonomer AA-6 manufactured by Toa Kosei Co., Ltd. (Polymethyl methacrylate with terminal methacryl group), AS-6 (Polystyrene with methacryl group as terminal group), AN-6S (Benzene with methacryl group as terminal group) Copolymer of ethylene and acrylonitrile), AB-6 (polybutyl acrylate with terminal methacryl group), Placcel FM5 (formerly manufactured by Daicel Chemical Industry Co., Ltd.) Ε-caprolactone 5 mol-equivalent addition product of 2-hydroxyethyl acrylate), FA10L (ε-caprolactone 10 mol-equivalent addition product of 2-hydroxyethyl acrylate), and Japanese Patent Laid-Open No. 2- Polyester-based macromonomers and the like described in Japanese Patent No. 272009. Among these macromonomers, particularly from the viewpoints of dispersibility, dispersion stability of the pigment dispersion, and developability exhibited by a coloring composition using the pigment dispersion, particularly preferred are those having flexibility and excellent solvent solubility. The polyester-based macromonomer is particularly preferably a polyester-based macromonomer represented by the polyester-based macromonomer described in Japanese Patent Laid-Open No. 2-272009.

The block polymer having a fixed portion on the surface of the pigment is preferably a block polymer described in Japanese Patent Laid-Open No. 2003-49110, Japanese Patent Laid-Open No. 2009-52010, and the like.

The pigment dispersant usable in the present invention can also be obtained as a commercial product. Examples of such specific examples include: "DA-7301" manufactured by Nanki Chemical Co., Ltd., and "Disperbyk-101 (Polyamine-Amine Phosphate)" manufactured by BYK Chemie. ), Disperbyk-107 (carboxylic acid ester), Disperbyk-110, Disperbyk-111 (acid-containing copolymer), Dis Disperbyk-130 (Polyamine), Disperbyk-161, Disperbyk-162, Disperbyk-163, Dispar Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170 (Polymer Copolymer) '', `` Bi BYK-P104, BYK-P105 (High Molecular Weight Unsaturated Polycarboxylic Acid) "," EFKA 4047, EFKA 4050 "manufactured by EFKA EFKA 4010, EFKA 4165 (polyurethane series), EFKA 4330 ~ EFKA 4340 (block copolymer), EFKA EFKA 4400 ~ EFKA 4402 (modified polyacrylate), EFKA 5010 (polyesteramine), EGKA Card (EFKA) 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 (fatty acid polyester), Efka (EFKA) 6745 (phthalocyanine derivative), Efka (EFKA) 6750 (even Nitrogen pigment derivative) "," Ajisper PB821 "," Ajisper PB822 "," Ajisper PB880 "," Ajinomoto Fine-Techno "manufactured by Ajinomoto Fine-Techno "Ajisper PB881", "Flowlen TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "Polyflow No. 50E, Polyflot (Polyflow) No. 300 (acrylic copolymer) "," Disperlon KS-860, Disperlon 873SN, Disperlon 874, Disperlon Disperlon # 2150 (aliphatic polycarboxylic acid), Disperlon # 7004 (polyetherester), Disperlon DA-703-50, Disperlon ) DA-705, Disperlon DA-725 '', `` Demol RN '', `` Demol N '' (formalin naphthalene sulfonate formalin polycondensate) manufactured by Kao Corporation, Demol (Demol) MS, Demol C, Demol SN-B (Aromatic Sulfonic Formalin Polycondensate) '', `` Homogenol L-18 (Polymer Polycarboxylate) Acid) "," Emulgen 920, Emulgen 930, Emulgen 935, Emulgen 985 (polyoxyethylene nonylphenyl ether) "," Aceta Acetamin 86 (stearylamine acetate) "," Solsperse 5000 (phthalocyanine derivative), Solsperse (Solsperse), manufactured by Lubrizol (Japan) ) 22000 (Azo Pigment Derivatives), Solsperse 13240 (Polyesteramine), Sonu Solsperse 3000, Solsperse 17000, Solsperse 27000 (polymer with functional part at the end), Solsperse 24000, Solsperse ) 28000, Solsperse 32000, Solsperse 38500 (graft polymer) "," Nikkol T106 (Polyoxyethylene Ethyl Sorbate) "manufactured by Nikko Chemical Co., Ltd. Monooleate), Nikkol MYS-IEX (polyoxyethylene monostearate) ", Hinoact T-8000E manufactured by Kawaken Chemical Co., Ltd., etc., Organic silicone polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., "W001: Cationic Surfactant" manufactured by Yushang Co., Ltd., polyoxyethyl lauryl ether, polyoxyethyl stearyl ether, polyoxyethyl oleyl ether, polyoxyethylene Non-ionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. , "W004, W005, W017" and other anionic surfactants, "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 '', Sannopco (shares ) Manufactured by `` Disperse-aid 6, Disperse-aid 8, Disperse-aid 15, Disperse-aid 15, Disperse-aid) 9100 "and other polymer dispersants," Adeka Pluronic L31 "," Adeka Pluronic "F38," Adeco Pro "manufactured by ADEKA Co., Ltd. Adeka Pluronic L42, Eddie Copro Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72 , Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pluronic (Adeka Pluronic) P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic Pluronic L121, Adeka Pluronic P-123 ", and" Eonet (trade name) S-20 "manufactured by Sanyo Chemical Co., Ltd., etc.

These pigment dispersants may be used alone or in combination of two or more. In the present invention, a pigment derivative and a polymer dispersant are preferably used in combination. In addition, the pigment dispersant may be used in combination with an alkali-soluble resin together with a terminally modified polymer, a graft polymer, and a block polymer having a fixed portion on the surface of the pigment. Examples of the alkali-soluble resin include (meth) acrylic acid copolymer, itaconic acid copolymer, butene acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. The acidic cellulose derivative is particularly preferably a (meth) acrylic acid copolymer. The N-position substituted maleimide imide monomer copolymer described in Japanese Patent Laid-Open No. 10-300922, the ether dimer copolymer described in Japanese Patent Laid-Open No. 2004-300204, and Japanese Patent Laid-Open No. The alkali-soluble resin containing a polymerizable group described in Japanese Patent No. 7-319161 is also preferable. Specific examples include an alkali-soluble resin: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer.

When a pigment dispersant is contained in the coloring composition, the total content of the pigment dispersant is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and more preferably 100 parts by mass of the pigment. It is 20 to 40 parts by mass.

The composition of the present invention may contain only one type of pigment dispersant, or may contain two or more types. When it contains two or more types, it is preferable that the total amount is the said range.

Specifically, if a polymer dispersant is used, The material is 100 parts by mass, and its use amount is preferably in the range of 5 to 100 parts by mass, more preferably in the range of 10 to 80 parts by mass.

When the pigment derivative is used in combination, the amount of the pigment derivative used is preferably within a range of 1 to 30 parts by mass, and more preferably 3 parts by mass relative to 100 parts by mass of the pigment. Within a range of from 20 parts by mass to 20 parts by mass, it is particularly preferably within a range of from 5 parts by mass to 15 parts by mass.

In the coloring composition, from the viewpoint of curing sensitivity and color concentration, the total of the content of the colorant and dispersant component is preferably 50% by mass or more and 90% by mass or less with respect to the total solid content constituting the coloring composition. It is more preferably 55 mass% or more and 85% by mass or less, and still more preferably 60 mass% or more and 80 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, and Mw is preferably 5000 to 100,000. The Mn is preferably 1,000 to 20,000.

The weight average molecular weight of the compound used in the present invention is defined by a polystyrene conversion value obtained by GPC measurement. The weight-average molecular weight and the number-average molecular weight can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0mm ID × 15.0cm) As a column, a 10 mmol / L lithium bromide N-methyl pyrrolidinone (NMP) solution was used as the eluent.

The alkali-soluble resin can be appropriately selected from the following alkali-soluble resins, which are linear organic macromolecular polymers, and The olefinic copolymer and the styrene-based copolymer have at least one group which promotes alkali solubility among the molecules). From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred from the viewpoint of controlling the developability. Specifically, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfonic acid group, and a phenolic hydroxyl group. It is preferably soluble in an organic solvent and can be developed with a weakly alkaline aqueous solution. As the group, a (meth) acrylic group is particularly preferred. These acid groups may be only one kind, or two or more kinds.

Examples of the monomer capable of imparting an acid group after polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and monomers having an epoxy group such as glycidyl (meth) acrylate. And monomers having an isocyanate group such as ethyl (meth) acrylate-2-isocyanate. These monomers for introducing an acid group may be only 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 "a monomer for introducing an acid group") may be used. The polymerization may be performed as a monomer component.

When an acid group is introduced as a monomer component using a monomer capable of imparting an acid group after polymerization, it is necessary to perform a treatment for imparting an acid group as described below after the polymerization.

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

The linear organic polymer used as the alkali-soluble resin is preferably a polymer having a carboxylic acid on a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a butene acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenol resins such as novolac resins, etc., acidic cellulose derivatives with carboxylic acids on the side chains, addition of polymers with hydroxyl groups Made from acid anhydride. In particular, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Ester, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate , Toluene (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of vinyl compounds include styrene, α-methylstyrene, vinyl toluene, and methacrylic acid Glycidyl ester, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., Japanese Patent Laid-Open No. 10 N-phenylmaleimide, N-cyclohexylmaleimide, and the like described in N-300922 as an N-substituted maleimide imine monomer. Furthermore, the other monomers copolymerizable with (meth) acrylic acid may be only one kind, or two or more kinds thereof.

The alkali-soluble resin also preferably contains a polymer (a), and the polymer (a) It is obtained by polymerizing a monomer component that requires a compound represented by the following general formula (ED) (hereinafter sometimes referred to as "ether dimer").

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.

Thereby, the colored composition of this invention can form the hardened coating film which is excellent in heat resistance and transparency. In the general formula (1) representing the 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 examples thereof include methyl and ethyl Alkyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, third pentyl, stearyl, lauryl, 2-ethylhexyl and other straight or branched alkyl groups Aryl groups such as phenyl; cyclohexyl, third butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl, etc. Formula groups; 1-methoxyethyl, 1-ethoxyethyl and other alkoxy-substituted alkyl groups; benzyl and other aryl-substituted alkyl groups and the like. Among these groups, particularly in terms of heat resistance, preferred are substituents of primary or secondary carbons, such as methyl, ethyl, cyclohexyl, benzyl, etc., which are not easily removed by acid or heat.

Specific examples of the ether dimer include, for example, dimethyl-2,2 '-[oxy Bis (methylene)] bis-2-acrylate (dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate), diethyl-2,2'-[oxybis (methylene )] Bis-2-acrylate, bis (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (isopropyl) -2,2' -[Oxybis (methylene)] bis-2-acrylate, bis (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (iso Butyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (third butyl) -2,2'-[oxybis (methylene)] bis -2-acrylate, bis (third pentyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (stearyl) -2,2'-[oxy Bis (methylene)] bis-2-acrylate, bis (lauryl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (2-ethylhexyl) ) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (1-methoxyethyl) -2,2'-[oxybis (methylene)] Bis-2-acrylate, bis (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, dibenzyl-2,2'-[ Oxybis (methylene)] bis-2-acrylate, diphenyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, dicyclohexyl-2,2' -[ Oxybis (methylene)] bis-2-acrylate, bis (third butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis ( Dicyclopentadienyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (tricyclodecyl) -2,2'-[oxybis (methylene )] Bis-2-acrylate, bis (isobornyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, diadamantyl-2,2'-[ Oxybis (methylene)] bis-2-acrylate, bis (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-acrylic acid Esters, etc. Among these specific examples, dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diethyl-2,2'-[oxybis (sub. (Meth)] bis-2-acrylate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, dibenzyl-2,2'-[oxybis (Methylene )] Bis-2-acrylate. These ether dimers may be only one kind, or two or more kinds. The structure derived from the compound represented by the general formula (ED) may copolymerize other monomers.

In order to improve the crosslinking efficiency of the colored composition of the present invention, it is preferred 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) acrylic group, an allyloxyalkyl group, or the like in a side chain is useful.

Examples of the polymer containing a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH) ), Manufactured by Diamond Shamrock Co. Ltd., Biscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Placcel CF200 series (all made by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (Daicel UCB) limited shares Company)). The alkali-soluble resin containing a polymerizable group is preferably a resin containing a polymerizable double bond modified by a urethane, and one of the resins is left by reacting an isocyanate group with an OH group in advance. An unreacted isocyanate group-containing (meth) acrylfluorene-based compound is obtained by reacting with a carboxyl group-containing acrylic resin; an unsaturated group-containing acrylic resin is obtained by using a carboxyl group-containing acrylic resin and a molecule Obtained by the reaction of a compound having an epoxy group and a polymerizable double bond; an acid pendant epoxy acrylate tree Grease; acrylic double resin containing a polymerizable double bond obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond; acrylic resin containing an OH group, an isocyanate, and a polymer having a polymerizable group Resin formed by the reaction of a compound; a resin obtained by subjecting the following resins to alkaline treatment described in Japanese Patent Laid-Open No. 2002-229207 and Japanese Patent Laid-Open No. 2003-335814, which are on a side chain An ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or the β-position.

The alkali-soluble resin is particularly preferably a benzyl (meth) acrylate / (meth) acrylic copolymer or a multi-component copolymer comprising benzyl (meth) acrylate / (meth) acrylic acid / other monomers. Other examples include a copolymer of benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid 2-hydroxyethyl ester copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate 2, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-acrylic acid described in Japanese Patent Laid-Open No. 7-140654 3-phenoxypropyl ester / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methacrylic acid Methyl ester / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc., particularly, benzyl methacrylate / formyl Copolymer of acrylic acid and the like.

The alkali-soluble resin can refer to paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to [0685] to [0700] of the specification of US Patent Application Publication No. 2012/0235099), The content is incorporated into the specification of this application.

It is more preferable to use the following resins: the copolymer (B) described in paragraph number 0029 to paragraph number 0063 described in Japanese Patent Laid-Open No. 2012-32767 and the alkali-soluble resin used in the examples, and Japanese Patent Laid-open No. 2012 The adhesive resins described in paragraph number 0088 to paragraph number 0098 of Japanese Patent Publication No. -208474 and the binder resins used in the examples, and the adhesives described in paragraph number 0022 to paragraph number 0032 of Japanese Patent Laid-Open No. 2012-137531 Resins and binder resins used in the examples, binder resins described in paragraph number 0132 to paragraph 0143 of Japanese Patent Laid-Open No. 2013-024934, binder resins used in the examples, binder resin used in the examples, Japanese Patent Laid-Open No. 2011- The adhesive resins described in paragraph number 0094 to paragraph number 0098 of 242752 and the examples, and the binder resins described in paragraph numbers 0030 to paragraph 0072 of Japanese Patent Laid-Open No. 2012-032770. These contents are incorporated into the specification of this application. More specifically, the following resins are preferred.

[Chemical 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, and most 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 even more preferably 7,000 to 20,000.

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

The composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds, preferably contains two or more kinds, and more preferably at least one kind has a polymerizable group. When it contains two or more types, it is preferable that the total amount is the said range.

<Other ingredients>

The coloring composition of the present invention may contain, in addition to the above-mentioned components, a surfactant, a cross-linking agent, a polymerization inhibitor, an organic carboxylic acid, an organic carboxylic anhydride, and the like within a range that does not impair the effects of the present invention. Other ingredients.

<< Interactive Agent >>

To the coloring composition of the present invention, various surfactants may be added from the viewpoint of further improving the coating properties. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, since the colored composition of the present invention contains a fluorine-based surfactant, the solution characteristics (especially fluidity) when the coating liquid is prepared are further improved, so that Further improve the uniformity or liquid saving of the coating thickness.

That is, when a film is formed using a coating liquid using a coloring composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the The wettability is improved, and the coatability to the surface to be coated is improved. Therefore, even when a thin film of about several micrometers (μm) is formed with a small amount of liquid, it is effective to form a film with a uniform thickness with small thickness unevenness more effectively.

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

Examples of the fluorine-based surfactant include: Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141 , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (the above are manufactured by DIC), Fluorad FC430, Ferox Fluorad FC431, Fluorad FC171 (the above are made by Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104 、 Surflon SC-105 、 Surflon SC1068 、 Surflon SC-381 、 Surflon SC-383 、 Surflon S393 、 Surflon KH-40 (the above are manufactured by Asahi Glass).

Specific examples of non-ionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates such as propoxylated glycerol and ethoxylated glycerol. Etc.), polyoxyethyl lauryl ether, polyoxyethyl stearyl ether, polyoxy ethyl ole alkenyl ether, polyoxy ethyl octyl phenyl ether, polyoxy ethyl nonyl Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, Pluronic L31, manufactured by BASF) , Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol, Japan ) (Shares)) and so on.

Specific examples of the cationic surfactant include: a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Industries, Ltd.), and an organosiloxane polymer KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.) , (Meth) acrylic (co) polymers Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (Kyoeisha Chemical ( Manufacturing), W001 (manufacturing by Yushang)

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

Examples of the silicone-based surfactant include: "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone" manufactured by Toray-Dow corning Co., Ltd. Toray Silicone DC11PA "," Toray Silicone SH21PA "," Toray Silicone SH28PA "," Toray Silicone SH29PA "," Toray Silicone Ketone (Toray Silicone SH30PA "," Toray Silicone SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4445 "manufactured by Momentive Performance Materials "TSF-4460", "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Silicone Co., Ltd., "BYK 307" manufactured by BYKChemie, "BYK 323", "BYK 330", etc.

When a surfactant is contained in the coloring composition of the present invention, the added amount of the surfactant is preferably 0.001% to 2.0% by mass, and more preferably 0.05% to 1.0% relative to the total mass of the coloring composition. quality%.

The composition of the present invention may contain only one type of surfactant, or may contain two or more types. When it contains two or more types, it is preferable that the total amount is the said range.

<< Crosslinking Agent >>

The coloring composition of the present invention may be supplemented with a crosslinking agent to further increase the hardness of a cured film obtained by curing the coloring composition.

The crosslinking agent is not particularly limited as long as it can harden the film by a crosslinking reaction. Examples include: (a) epoxy resin; (b) melamine compounds, guanamine compounds, and glycoluril compounds substituted with at least one substituent selected from methylol, alkoxymethyl, and methyloxymethyl. (glycoluryl compound) or urea compound; (c) a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a hydroxymethyl group, an alkoxymethyl group, and a methyloxymethyl group. Among these, a polyfunctional epoxy resin is preferable.

For details such as specific examples of the cross-linking agent, refer to the descriptions in paragraphs 0134 to 0147 of Japanese Patent Laid-Open No. 2004-295116.

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

The composition of the present invention may contain only one type of crosslinking agent, or may contain two or more types. When it contains two or more types, it is preferable that the total amount is the said range.

<< polymerization inhibitor >>

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

Examples of polymerization inhibitors usable in the present invention include hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, third-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), N- Nitrophenylhydroxylamine cerium salt and the like.

When a polymerization inhibitor is contained in the coloring composition of the present invention, The mass of all the components and the addition amount of the polymerization inhibitor are preferably from 0.01% by mass to 5% by mass.

The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When it contains two or more types, it is preferable that the total amount is the said range.

<< Organic carboxylic acid, organic carboxylic anhydride >>

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

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, trimethylacetic acid, hexanoic acid, glycolic acid, acrylic acid, and methacrylic acid; oxalic acid, malonic acid, and amber Acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and other dicarboxylic acids, 1, Tricarboxylic acids such as 2,3-malonic acid and aconitic acid. Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group such as benzoic acid and phthalic acid is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to the carboxyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, are particularly preferred. For example, maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specifically, examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and malay. Acid anhydrides, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and other aliphatic carboxylic acids Acid anhydride. Examples of the aromatic carboxylic anhydride include: o Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalenedicarboxylic anhydride, etc. Among these, those having a molecular weight of 600 or less, especially those having a molecular weight of 50 to 500 are particularly preferred. Specific examples include maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride.

When an organic carboxylic acid and an organic carboxylic anhydride are contained in the coloring composition of this invention, the addition amount of an organic carboxylic acid and / or an organic carboxylic anhydride is 0.01 to 10 weight% of the total solid content, Preferably it is preferable 0.03 to 5% by weight, and more 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 anhydride, and may contain two or more kinds. When it contains two or more types, it is preferable that the total amount is the said range.

By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1,000 or less, high pattern adhesion can be maintained, and the remaining of undissolved matter of the coloring composition can be further reduced.

In addition to the additives, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like can be blended in the coloring composition as needed. Examples of the additives include those described in paragraphs 0155 to 0156 of Japanese Patent Laid-Open No. 2004-295116, and these contents are incorporated into the specification of the present application.

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

The composition of the present invention may contain only one of the above-mentioned components, or may contain two the above. When it contains two or more types, it is preferable that the total amount is the said range.

<Preparation method of coloring composition>

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

Moreover, when preparing a coloring composition, each component which comprises a coloring composition can be mix | blended at once, or each component can be mix | blended after dissolving and dispersing in a solvent. In addition, the input sequence or working conditions at the time of deployment are not particularly limited. For example, a composition can be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component can be appropriately prepared into two or more solutions and dispersions, and these components can be mixed during use (during coating). And prepared into a composition.

The coloring composition prepared as described above can be used after filtration and separation using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, more preferably a pore diameter of about 0.05 μm to 0.5 μm.

When a pigment is blended in the composition of the present invention, it is preferred to use a washed pigment. By using the washed pigment, foreign matter in the composition can be further reduced. For the method of cleaning the pigment, refer to paragraphs 0011 to 0099 of Japanese Patent Laid-Open No. 2010-83997, and the contents are incorporated into this specification.

The coloring composition of the present invention can be preferably used for forming a coloring layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film excellent in heat resistance and color characteristics, it can be preferably used to form a colored pattern (colored layer) of a color filter. In addition, the coloring composition of the present invention can be preferably used for a solid-state imaging device (such as a charge-coupled device (CCD), a complementary metal oxide semiconductor (Complementary Metal Oxide) (Semiconductor, CMOS), etc.) or color pattern forming such as color filters used in image display devices such as liquid crystal display devices (LCD). Furthermore, it can also be used suitably for the manufacture of printing inks, inkjet inks, and coatings. Among them, a color filter for a solid-state imaging element such as a CCD and a CMOS can be preferably used for production.

<Curable film, pattern forming method, color filter, and method for manufacturing color filter>

Next, the cured film, the pattern forming method, and the color filter of the present invention will be described in detail by a manufacturing method thereof.

The cured film of the present invention is obtained by curing the colored composition of the present invention. This cured film can be preferably used for a color filter.

The pattern forming method of the present invention applies the colored composition of the present invention to a support to form a colored composition layer, and removes unnecessary portions to form a colored pattern.

The pattern forming method of the present invention can be preferably used to form a colored pattern (pixel) included in a color filter.

The composition of the present invention can use a so-called photolithography method to produce a color filter by pattern formation, and can also form a pattern by a dry etching method.

That is, the first method of manufacturing a color filter of the present invention can be exemplified by a method of manufacturing a color filter including the steps of: applying a colored composition to a support to form a colored composition layer; and applying the coloring A step of exposing the composition layer in a pattern; and a step of developing and removing an unexposed portion to form a colored pattern.

In addition, the second method of manufacturing a color filter of the present invention can be exemplified by a method of manufacturing a color filter including the steps of applying a coloring composition to a support to form a coloring composition layer and hardening it to form A step of coloring a layer; a step of forming a photoresist layer on the coloring layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as etching Masking the dry etching step of the colored layer.

In the present invention, it is more preferably produced by a photolithography method.

These methods are described in detail below.

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

<< Procedure for Forming Colored Composition Layer >>

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

The support that can be used in this step can be, for example, a camera provided with a Charge Coupled Device (CCD) or a Complementary Metal-Oxide Semiconductor (CMOS) on a substrate (for example, a silicon substrate). Element (light receiving element) substrate for solid-state imaging element.

The colored pattern of the present invention may be formed on the imaging element formation surface side (front surface) of the solid-state imaging element substrate, or may be formed on the surface side (back surface) where the imaging element is not formed.

A light-shielding film may be provided between the colored patterns of the solid-state imaging element or on the back surface of the substrate for the solid-state imaging element.

In addition, if necessary, an undercoat layer may be provided on the support to improve the adhesion with the upper layer, prevent the diffusion of substances, or achieve planarization of the substrate surface. In the undercoat layer, a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like may be blended. These components are preferably self-blended into the composition of the invention The ingredients are appropriately selected.

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

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

<Procedure for Pattern Formation by Photolithography>

<< Procedure for exposure >>

In the exposing step, the colored composition layer formed in the colored composition layer forming step is subjected to pattern exposure using an exposure device such as a stepper, through a mask having a predetermined mask pattern. Thereby, a cured film can be obtained.

The radiation (light) that can be used during exposure is particularly preferably ultraviolet rays such as g-rays and i-rays (i-rays are particularly preferred). Irradiation amount (exposure amount) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 1000mJ / cm} 2, and particularly preferably ^{80mJ / cm 2 ~ 500mJ / cm} 2.

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

By setting the film thickness to 1.0 μm 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 μm or less may be preferably formed. By developing the obtained cured film using a pattern formation step described later, development properties can be obtained even for a thin film. , Color surface with excellent surface roughness suppression and pattern shape.

<< Developing steps >>

Then, an alkali developing treatment is performed, whereby the colored composition layer in a portion not exposed to light in the exposure step is eluted into the alkaline aqueous solution, and only the light-hardened portion remains.

The developing solution is preferably an organic alkali developing solution that does not damage the underlying imaging element, circuit, or the like. The development temperature is usually 20 ° C to 30 ° C, and the development time was previously 20 seconds to 90 seconds. In order to further remove the residue, in recent years, it is sometimes performed for 120 seconds to 180 seconds. Furthermore, in order to further improve the residue removal performance, the following steps may be repeated several times: the developing solution is shaken off every 60 seconds, and the developing solution is further supplied again.

Examples of the alkaline agent used in the developing solution include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutyl hydroxide. Organic basic compounds such as ammonium hydroxide, trimethylbenzyl ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the like may be preferably used. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water at a concentration of 0.001% to 10% by mass, and preferably 0.01% to 1% by mass is used as a developer. Shadow Liquid.

In addition, an inorganic base may be used in the developing solution. The inorganic base is preferably, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, or the like.

When a developer containing such an alkaline aqueous solution is used, it is usually washed (washed) with pure water after development.

Then, it is preferable to perform heat processing (post-baking) after performing drying. If colored patterns of multiple colors are formed, the steps can be repeated one by one for each color to produce a hardened film. Thereby, a color filter can be obtained.

Post-baking is a heat treatment after development for completely hardening, and it is usually heat-cured at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C.

The post-baking of the developed coating film may be performed in a continuous or batch manner using a heating mechanism such as a hot plate or a convection oven (hot-air circulation dryer), a high-frequency heater, and the like to satisfy the conditions. Bake processing.

<Case where pattern is formed by dry etching method>

The dry etching can be performed on the colored layer using a patterned photoresist layer as a mask and using an etching gas. Specifically, a photoresist layer is formed by coating a colored layer with a positive-type or negative-type radiation-sensitive composition and drying it. In the formation of the photoresist layer, it is preferable to further perform a pre-baking treatment. The photoresist formation process is particularly preferably in the form of performing a heat treatment (Post-Exposure Bake (PEB)) after exposure and a heat treatment (post-baking treatment) after development.

As the photoresist, for example, a positive radiation-sensitive composition can be used. The positive radiation-sensitive composition can be induced ultraviolet (g-ray, h-ray, i-ray), A positive resist composition suitable for a positive-type photoresist, which contains radiation such as far-infrared ultraviolet rays of an excimer laser, an electron beam, an ion beam, and X-rays. Among the radiations, g-rays, h-rays, and i-rays are preferable, and i-rays are preferable.

Specifically, the positive radiation-sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin uses the following conditions: The quinonediazide group is decomposed to generate a carboxyl group by irradiation with light having a wavelength of 500 nm or less, and the result changes from an alkali-insoluble state Alkali soluble. The positive photoresist has excellent resolving power, so it can be used to fabricate integrated circuits such as integrated circuits (ICs) or large scale integrated circuits (LSIs). Examples of the quinonediazide compound include naphthoquinonediazide compounds. Examples of commercially available products include "FHi622BC" (manufactured by Fujifilm Electronic Materials).

The thickness of the photoresist layer is preferably 0.1 μm to 3 μm, preferably 0.2 μm to 2.5 μm, and further preferably 0.3 μm to 2 μm. In addition, the photoresist layer can be preferably coated by using the coating method of the coloring layer described above.

Then, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a resist through-hole group. The formation of the resist pattern is not particularly limited, and a conventionally known photolithography technique can be appropriately optimized and performed. A resist through-hole group is provided in the photoresist layer by exposure and development, thereby setting a resist pattern as an etching mask used in subsequent etching on the colored layer.

The exposure of the photoresist layer can be performed by: blocking a predetermined mask In a pattern, g-rays, h-rays, i-rays, etc., and preferably i-rays are used for exposing the positive or negative radiation-sensitive composition. After the exposure, the photoresist is removed corresponding to the area where a colored pattern is to be formed by performing a development process using a developing solution.

The developer can be used as long as it does not affect the colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, various organic solvents can be used. Combination or alkaline aqueous solution. The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound at a concentration of 0.001% to 10% by mass, and preferably 0.01% to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc. In the case where an alkaline aqueous solution is used as the developing solution, a washing treatment is usually performed with water after development.

Then, the resist pattern is used as an etching mask, and patterning is performed by dry etching so that a through-hole group is formed in the colored layer. Thereby, a colored pattern is formed. The through-hole groups are arranged in a checkerboard pattern in the colored layer. Therefore, the first coloring pattern in which the through-hole group is provided in the coloring layer has the first coloring pixels having a plurality of square shapes in a checkerboard shape.

Specifically, in the dry etching, the colored layer is dry-etched using the resist pattern as an etching mask. Representative examples of dry etching include Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. 59-46628, Japanese Patent Laid-Open No. 58-9108, Japanese Patent Laid-Open No. 58-2809, and Japanese Patent Laid-Open No. Show The methods described in various publications such as 57-148706 and Japanese Patent Laid-Open No. 61-41102.

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

It is preferable to include a first-stage etching, a second-stage etching, and an over-etching. The first-stage etching uses a mixed gas of a fluorine-based gas and oxygen (O ₂ ) to perform etching until the support is not exposed. Up to the region (depth), and after the first-stage etching, the mixed gas is etched using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) until the area where the support is exposed is preferred. Up to (depth), the over-etching is performed after the support is exposed. Hereinafter, the specific method of dry etching, the etching in the first step, the etching in the second step, and the over-etching will be described.

Dry etching is performed by obtaining the etching conditions in advance by the following method.

(1) The etching rate (nm / min) of the first-stage etching and the etching rate (nm / min) of the second-stage etching are calculated, respectively. (2) Calculate the time for the thickness required for etching in the first-stage etching and the time for the thickness required for etching in the second-stage etching, respectively. (3) The first-stage etching is performed in accordance with the etching time calculated in the above (2). (4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Alternatively, the etching time is determined by end point detection, and the second-stage etching is performed based on the determined etching time. (5) The overetching time is calculated with respect to the total time of said (3) and (4), and overetching is performed.

From the viewpoint of processing the organic material to be etched into a rectangular shape, the mixed gas used in the first-stage etching step preferably contains a fluorine-based gas and oxygen (O ₂ ). In addition, by setting the etching step in the first step to a form in which the support is not exposed, damage to the support can be avoided. In addition, from the viewpoint of avoiding damage to the support, it is preferable that the second-stage etching step and the over-etching step be performed by using a mixed gas of a fluorine-based gas and oxygen in the first-stage etching step. After the support is not exposed, an etching process is performed using a mixed gas of nitrogen and oxygen.

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

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

Then, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes the steps of applying a peeling solution or a solvent to the resist pattern to adjust the resist pattern to a removable state; and A step of removing the resist pattern with washing water.

The step of applying a peeling solution or a solvent to the resist pattern and adjusting the resist pattern to a removable state may be performed, for example, by applying a peeling solution or a solvent to the resist pattern at least for a predetermined period of time. Steps of immersion development. The time for which the peeling solution or the solvent is stagnation 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 may include, for example, a step of removing the resist pattern by spraying the washing pattern on the resist pattern from a spray nozzle or a spray nozzle. As the washing water, pure water is preferably used. Examples of the spray nozzle include a spray nozzle that includes the entire support in its spray range, or a spray nozzle that is a movable spray nozzle and whose movable range includes the entire support. When the spray nozzle is movable, in the step of removing the resist pattern, the cleaning pattern can be moved more than twice from the center of the support to the end of the support to spray the washing water, thereby removing the resist pattern more effectively. .

The peeling liquid usually contains an organic solvent, and may further contain an inorganic solvent. Examples of the organic solvent include: 1) a hydrocarbon compound, 2) a halogenated hydrocarbon compound, 3) an alcohol compound, 4) an ether or acetal compound, 5) a ketone or aldehyde compound, 6) an ester compound, 7) Polyol-based compounds, 8) carboxylic acids or their anhydride-based compounds, 9) phenol-based compounds, 10) nitrogen-containing compounds, 11) sulfur-containing compounds, and 12) fluorine-containing compounds. The peeling liquid preferably contains a nitrogen-containing compound, and more preferably contains a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, Diethanolamine, triethanolamine, and the like are preferably monoethanolamine, diethanolamine, and triethanolamine, and more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α-formyl Pyridine, β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, etc., preferably N-methyl-2-pyrrolidone N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The peeling liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine as the non-cyclic nitrogen-containing compound and as a ring. The nitrogen-containing compound is at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethylmorpholine, and further preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

When the removal is performed using a stripping solution, the resist pattern 52 formed on the first colored pattern 12 may be removed, and even if a deposit is formed as an etching product on the sidewall of the first colored pattern 12. In some cases, the deposits may not be completely removed. The so-called deposits refer to those obtained by attaching and depositing etching products on the side walls of the colored layer.

The content of the peeling liquid is preferably 9 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the non-cyclic nitrogen-containing compound, and The content of 100 parts by mass of the cyclic nitrogen-containing compound is 65 parts by mass or more and 70 parts by mass or less. The peeling liquid is preferably one obtained by diluting a mixture of the non-cyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

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

When the colored composition of the present invention is used, for example, clogging of a nozzle or a piping portion of a spraying portion of a coating device, or adhesion, sedimentation, or drying of a colored composition or a pigment in a coating machine may occur. Pollution. Therefore, in order to efficiently clean the contamination caused by the colored composition of the present invention, it is preferable to use a solvent related to the present composition described above as a cleaning liquid. In addition, Japanese Patent Laid-Open No. 7-128867, Japanese Patent Laid-Open No. 7-146562, Japanese Patent Laid-Open No. 8-278637, Japanese Patent Laid-Open No. 2000-273370, and Japanese Patent Laid-Open No. 2006-85140 The cleaning fluids described in the Gazette, Japanese Patent Laid-Open No. 2006-291191, Japanese Patent Laid-Open No. 2007-2101, Japanese Patent Laid-Open No. 2007-2102, Japanese Patent Laid-Open No. 2007-281523, and the like can also be compared. It is preferably used for cleaning and removing the colored composition of the present invention.

Among these, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

These solvents may be used alone or in combination of two or more. To mix the two with In the above case, 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 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. Particularly preferred is a mixed solvent of Propyleneglycol monomethylether acetate (PGMEA) and Propyleneglycol monomethylether (PGME), and the ratio thereof is 60/40. Furthermore, in order to improve the permeability of the cleaning solution to the pollutants, a surfactant related to the composition described above may be added to the cleaning solution.

Since the color filter of the present invention uses the coloring composition of the present invention, it can perform exposure with excellent exposure margin, and the pattern shape of the coloring pattern (coloring pixel) formed is excellent, and the pattern surface is rough or Since the residue in the developing section is suppressed, the color characteristics are excellent.

The color filter of the present invention can be preferably used for solid-state imaging elements such as CCD and CMOS, and is particularly suitable for high-resolution CCD or CMOS with a resolution of more than 1 million pixels. The color filter for a solid-state imaging element of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixels) of the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less.

The size (pattern width) of the colored pattern (colored pixels) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.7 μm or less.

<Solid-state image sensor>

The solid-state imaging element of the present invention includes the color filter of the present invention described above. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device, and examples thereof include the following configurations.

The solid-state imaging element has a structure including a plurality of photodiodes on a support and constituting a light-receiving area of the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.), and transmission including polycrystalline silicon and the like. An electrode having, on the photodiode and the transmission electrode, a light-shielding film containing tungsten or the like that has only the light-receiving portion of the photodiode opening, and a method of covering the entire surface of the light-shielding film and the light-diode receiving portion The formed element protective film containing silicon nitride or the like has the color filter for a solid-state imaging element of the present invention on the element protective film.

Furthermore, it may be a structure having a light condensing mechanism (for example, a micro lens, etc., the same below) on the element protective layer and below the color filter (the side close to the support), or on the color filter. The structure of the light-concentrating mechanism.

<Image display device>

The color filter of the present invention can be used not only for the solid-state imaging element, but also for an image display device such as a liquid crystal display device or 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 having a good hue and excellent display characteristics.

The definition of the display device or the details of each display device is described in, for example, "Electronic Display Elements (Azawa Sasaki, Industrial Survey Association (Stock), 1990 (Published annually) "," Display components (Ibuki Shun-cho, Industrial Books (Stock), published in the Heisei year) "and so on. The liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Survey Society (Stock), issued in 1994)". The liquid crystal display device applicable to the present invention is not particularly limited. For example, the liquid crystal display device can be applied to various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention can also be used in a liquid crystal display device of a color thin film transistor (Thin Film Transistor, TFT) system. The color TFT-type liquid crystal display device is described in, for example, "color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". Furthermore, the present invention can also be applied to liquid crystal displays with enlarged viewing angles such as in-plane switching (IPS) and other horizontal electric field driving methods, and multi-domain vertical alignment (MVA) pixel segmentation methods. Device or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching (Fringe Field Switching (FFS) and Reflective-Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention can also be used in a bright and high-definition color-filter on array (COA) method. In a COA-type liquid crystal display device, in addition to the general required characteristics described above, the required characteristics of the color filter layer may also require the required characteristics of the interlayer insulating film, that is, low dielectric constant and resistance. Peeling liquid. In the color filter of the present invention, since a pigment polymer having an excellent hue is used, color purity, light transmittance, and the like are good, and a colored pattern (paint It is possible to provide a liquid crystal display device of the COA system with high color tone and excellent long-term durability due to its excellent hue. Furthermore, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

About these image display methods, for example, are described in "Electroluminescence (EL), Plasma Display Panel (PDP), Liquid Crystal Display (LCD) displays-the latest technology and market Trends-(Toray Research Center Investigation and Research Department, issued in 2001) "on page 43 and so on.

In addition to the color filter of the present invention, the liquid crystal display device provided with the color filter of 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 ensuring film. . The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. About these components, for example, it is described in "'94 Liquid Crystal Display Peripheral Material-Chemicals Market (Kentaro Shima, CMC (Stock), issued in 1994)", "Current Status and Future Outlook of Liquid Crystal Related Markets in 2003 (Volume 2)" (Table Liangji, Fuji Camry Research Institute (shares), issued in 2003) ".

Regarding the backlight, it is described in "SID meeting Digest" (1380 (2005)) (A. Konno et al.) Or the December 2005 issue of the monthly monitor, page 18 ~ 24 pages (Kojima Shima) and 25 to 30 pages of the literature (Takaaki Yagi).

If the color filter of the present invention is used for a liquid crystal display device, high contrast can be achieved when combined with a conventionally known three-wavelength tube of a cold-cathode tube. By setting red, green, and blue LED light sources (RGB-LEDs) as the backlight, a liquid crystal display device with high brightness and good color reproducibility can be provided.

[Example]

The following examples illustrate the present invention in more detail. The materials, usage amounts, proportions, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

In addition, unless otherwise specified, "%" and "part" are the basis of quality.

Synthesis example of pigment polymer

The following xanthracene 1 to xanthracene 4 are included in a preferable aspect (A1) of the pigment polymer. The following xanthracene 5 is included in a preferable aspect (A2) of the pigment polymer. The following xanthracene 6 is included in a preferable aspect (A3) of the pigment polymer. The following xanthenes 7 and xanthones 8 are included in the preferred embodiment (A4) of the pigment polymer.

<Synthesis of Xanthene 1>

After dissolving 20.0 g (41.8 mmol) of Rhodamine B in 125 g of chloroform, 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling in an ice bath. Thereafter, it was heated at an external temperature of 65 ° C for 3 hours. After cooling to 20 ° C, 9.8 g (75.2 mmol) of 2-hydroxyethyl methacrylate was added while cooling with an ice bath, and 30.8 g (304 mmol) of triethylamine was added. The internal temperature was adjusted to 20 ° C, and after stirring for 3 hours, 100 g of chloroform was added. After separating with water, the chloroform layer was concentrated. The obtained concentrate was added to 100 mL of methanol, and 16.4 g (41.8 mmol) of tetrabutylammonium trifluoromethanesulfonate was added. Liquid separation was performed with 200 mL of ethyl acetate and 100 mL of water, and the ethyl acetate layer was concentrated to obtain 18.0 g of monomer X.

In a three-necked flask, monomer X (8.2 g), 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 heated to 80 ° C under a nitrogen atmosphere. To this solution, monomer X (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), and 2,2'-azobis (isobutyric acid) diamine were added dropwise over 5 hours. A mixed solution of methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 10 hours, the temperature was raised to 80 ° C, and after heating and stirring for 3 hours, it was left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL to perform reprecipitation. After air-drying at 40 ° C for 2 days, 7.5 g of a pigment polymer (xanthracene 1) was obtained.

The weight average molecular weight (Mw) of the pigment polymer (xanthracene 1) confirmed by GPC measurement was 10,700. The acid value was 37 mgKOH / g by titration using a 0.1 N sodium hydroxide aqueous solution.

<Synthesis of Xanthene 2 ~ Xanthene 4>

A dye polymer (xanthracene 2 to xanthracene 4) was synthesized by performing the same operation except that the counter anion of monomer X in Synthesis Example 1 was changed as described in the following table.

<Synthesis of Xanthene 5>

The following monomers (67 mol% of xanthene monomers and 33 mol% of methacrylic acid) were copolymerized to synthesize xanthracene 5.

After dissolving 28927.4 g (41.8 mmol) of C.I. Acid Red in 125 g of chloroform, 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling with an ice bath. Then, it stirred at the external temperature of 65 degreeC for 3 hours. After cooling to 20 ° C, 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. Adjust the internal temperature to 20 ° C and stir After stirring for 3 hours, 100 g of chloroform was added, and after separating with water, the chloroform layer was concentrated to obtain 15.0 g of monomer Z. Furthermore, at this time, 10.0 g of the monomer Z2 was obtained from the aqueous layer.

In a three-necked flask, monomer Z (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, monomer Z (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), and 2,2'-azobis (isobutyric acid) diamine were added dropwise over 4 hours. A mixed solution of methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 4 hours, the temperature was raised to 93 ° C, and after heating and stirring for 2 hours, it was left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL to perform reprecipitation. After air-drying at 40 ° C for 2 days, 7.4 g of a pigment polymer (xanthracene 5) was obtained.

The weight average molecular weight (Mw) of the pigment polymer (xanthracene 5) confirmed by GPC measurement was 10,000. The acid value was 38 mgKOH / g by titration using a 0.1 N sodium hydroxide aqueous solution.

<Synthesis of Xanthene 6>

Xanthane monomer Y 60mol% and methacrylic acid 40mol%

[Chemical 50]

20.0 g (41.8 mmol) of rose red B and 24.3 g (41.8 mmol) of the potassium salt of the following polymerizable anion were subjected to salt exchange in 200 ml of methanol, 1 L of water was added, and extraction was performed with 500 ml of chloroform, and concentrated to obtain 25 g Body Y.

In a 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, monomer Y (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), and 2,2'-azobis (isobutyric acid) diamine were added dropwise over 5 hours. A mixed solution of methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 5 hours, the temperature was raised to 93 ° C, and after heating and stirring for 2 hours, the mixture was left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL to perform reprecipitation. After air drying at 40 ° C for 2 days, 4.8 g of a pigment polymer (xanthracene 6) was obtained.

The weight average molecular weight (Mw) of the dye polymer (xanthracene 6) confirmed by GPC measurement was 10,000.

<Synthesis of Xanthene 7>

The following monomers (xanthracene monomer Z2 (64 mol%) and methacrylic acid (36 mol%)) were copolymerized to synthesize xanthracene 7.

In a three-necked flask, the monomer Z2 (8.2 g), methacrylic acid (0.46g), dodecyl mercaptan (0.255g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as "PGMEA") (23.3g), in a nitrogen atmosphere Heat to 80 ° C. To this solution, monomer Z2 (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), and 2,2'-azobis (isobutyric acid) diamine were added dropwise over 3 hours. A mixed solution of methyl ester [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.58 g) and PGMEA (23.3 g). After stirring for 4 hours, the temperature was raised to 90 ° C, and after heating and stirring for 2 hours, the mixture was left to cool to obtain a PGMEA solution of the intermediate (MD-1). After cooling, it was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL to perform reprecipitation. After air-drying at 40 ° C for 2 days, 7.8 g of a pigment polymer (xanthracene 7) was obtained.

The weight average molecular weight (Mw) of the dye polymer (xanthracene 7) confirmed by GPC measurement was 11,000. The acid value was 38 mgKOH / g by titration using a 0.1 N sodium hydroxide aqueous solution.

<Synthesis of Xanthene 8>

(Copolymer of the following monomers)

According to the method for producing a salt-forming compound (A-1) described in Japanese Patent Application Laid-Open No. 2011-242752, paragraph 0165, a pigment polymer (xanthracene 8) was obtained. The weight average molecular weight (Mw) of the dye polymer (xanthracene 7) confirmed by GPC measurement was 10,500.

[Chem 53]

Preparation of colored composition

Preparation of blue pigment dispersion

The blue pigment dispersion liquid 1 was prepared as follows.

A bead mill (zirconia beads, 0.3 mm in diameter) will contain 9.6 parts of CI Pigment Blue (Pigment Blue) 15: 6 (blue pigment, average particle size 55nm) and 3.2 parts as pigment dispersant A mixture of Disperbyk 111, 69.8 parts of PGMEA, and 17.4 parts of cyclohexanone was mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by Japan BEE Co., Ltd.) with a pressure-reducing mechanism was further used to perform the dispersion treatment at a flow rate of 500 g / min at a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion liquid 1 (CI Pigment Blue 15: 6 dispersion liquid, pigment concentration: 12.8% by mass) used in the coloring composition of Examples or Comparative Examples.

Preparation of Example 0

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

In addition, before Preparation Example 0, distillation using a solvent and drying agent were used to remove toluene and water from the system, and dyes and pigments were repeatedly applied with distilled water. Wash and dry to remove Na and K ions from the system. Raw materials such as other monomers are purified before use to remove impurities (toluene, Na ions, K ions, etc.) and then prepared.

The results obtained by measuring the concentrations of the following components in the composition of Example 0 are shown. The water content is measured by the Karl Fisher method according to a known method. Specifically, the moisture content of the measurement data was measured using a Karl Fischer moisture meter (KF-06 manufactured by Mitsubishi Chemical Holdings), and it was measured as a moisture content / quality of the measurement data × 100. Moisture content.

Moisture content: 0.005 mass% or less

Toluene concentration: 0.001ppm or less

Na ion concentration: 0.001ppm or less

K ion concentration: 0.001ppm or less

Water, toluene, a Na ion source (specifically, NaCl), and a K ion source (specifically, KCl) were added to the composition of Example 0 to prepare samples of Examples 1 to 6.

In addition, except that the pigment polymer, the curable compound (monomer), and the photopolymerization initiator were changed as shown in the following table, Examples 7 to 95 and Comparative Examples 1 to 16 were produced in the same manner as in Example 0. Composition.

Hardening compound (monomer (m-2))

Hardening compound (monomer (m-3))

Hardening compound (monomer (m-4))

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

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

<Evaluation of long-term stability over time (viscosity)>

The initial viscosity (Vi) of the compositions obtained in the examples and comparative examples was measured, and the contents were measured in a closed container at 5 ° C for 100 days. The viscosity (Vd) was measured over time. The value of | Vi-Vd | / Vi × 100% is calculated and evaluated based on this value. The results are shown in the following table.

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

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

2: Viscosity change rate is higher than 8% and less than 12% (out of tolerance)

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

Production of color filters using coloring composition

<Pattern formation>

The colored compositions of the examples and comparative examples prepared as described above were each coated on a glass substrate to form a colored composition layer (coating film). Then, a heat treatment (pre-baking) was performed on a 90 ° C. hot plate for 120 seconds so that the dry film thickness of the coating film was 0.6 μm.

<Long-term light resistance at low oxygen concentration>

The film-formed products (patterns) obtained in the examples and comparative examples were covered with a glass cover (in a hypoxic state where oxygen supply was blocked). Suga (a light resistance tester for a xenon lamp light source) SX75F manufactured by a suga) tester was irradiated at a light intensity of 10,000 lux for 200 hours to perform a light resistance test.

The color before and after irradiation was measured with MCPD-2000 manufactured by Otsuka Electronics Co., Ltd. The difference (ΔE * ab) was evaluated. The results are shown in the following table.

6: 0.5% or less (especially good)

5: Above 0.5% and below 1% (good)

4: Above 1% and below 2% (slightly good)

3: Above 2% and below 3% (within tolerance)

2: Above 3% and below 5% (out of tolerance)

1: higher than 5% (out of tolerance)

<Evaluation of defects after a long period of time (foreign substance increase rate evaluation)>

Each of the obtained radiation-sensitive compositions was coated on a silicon wafer so that the film thickness after coating became 0.6 μm, and then heated on a hot plate at 100 ° C. for 2 minutes to obtain a colored composition layer. .

A defect evaluation device ComPLUS (applied by Applied Materials) was used for the substrate on which the colored composition layer was formed, and foreign matter having a size of 1.0 μm or more was counted.

The evaluation was performed immediately after the colored composition was prepared and after refrigerated at 5 ° C. for one month, and the foreign substance increase rate was evaluated according to the following criteria.

The foreign substance increase rate was calculated as (the number of foreign substances after refrigerated at 5 ° C for one month / the number of foreign substances immediately after preparation). Practically, the determination criterion 3 or more is desirable. The results are shown in the table.

(Judgment criteria)

6: less than 1.1

5: 1.1 or more and less than 1.3

4: 1.3 or more and less than 1.5

3: 1.5 or more and less than 2.0

2: 2.0 or more and less than 3.0

1: 3.0 or more

<Long-term evaluation>

(Fabrication of Silicon Wafer with Undercoating)

Using a spin coater, a resist CT-4000L solution (manufactured by Fujifilm Electronic Materials (stock); base transparent agent) was coated on a silicon wafer so that the film thickness became 0.1 μm, and the temperature was 220 ° C. An undercoat was formed by heating and drying for 1 hour to obtain a silicon wafer with an undercoat.

(Creation of colored patterns)

The coloring compositions of the examples and comparative examples were applied on a silicon wafer with an undercoating layer by a spin coating method so that the film thickness after coating became 0.6 μm, and then on a hot plate at 90 ° C. It heated for 2 minutes, and obtained the coloring composition layer.

Next, an i-ray stepper exposure apparatus FPA-3000i5 + (manufactured by Canon) was used for the obtained colored composition layer, and an island-shaped pattern of 3.0 μm was exposed at 300 mj / cm ² through a barrier mask. Then, the exposed coloring composition layer was subjected to immersion development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, a spin shower was used for rinsing, and then water was washed with pure water to obtain a colored pattern.

Scanning Electron Microscope (SEM) (trade name: S-7800H, manufactured by Hitachi, Ltd.) was used to compare the obtained work. Observe the line width of the color pattern. The difference between the maximum value and the minimum value of the line width in one pixel in the case where the leaving time is 72 hours is measured at an arbitrary 10 points in the wafer and an average value is obtained. When the standing time is 0 hours, the average values in the examples and comparative examples are both <0.02 μm.

(Judgment criteria)

6: less than 0.02 μm (best)

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

4: 0.04 μm or more and less than 0.06 μm (slightly good)

3: 0.06 μm or more and less than 0.10 μm (within tolerance)

2: 0.10 μm or more and less than 0.20 μm (out of tolerance)

1: 0.20 μm or more (out of tolerance (worst))

<Defect evaluation after long-term humidity resistance test (evaluation of foreign matter increase rate)>

The composition of the Example and the comparative example was apply | coated on the silicon wafer so that the film thickness after application might become 0.6 micrometers, and it heated at 100 degreeC for 2 minutes on the hot plate, and obtained the coloring composition layer. Thereafter, full i-ray exposure was performed at an exposure amount of 1000 mJ / cm ² , and additional heating was performed on a hot plate at 200 ° C. for 10 minutes to prepare an initial sample.

A sample obtained by subjecting an initial sample to moisture resistance under conditions of 85 ° C. and 85% RH for 408 hours was used as a sample after the moisture resistance test.

For each sample, a defect evaluation device ComPLUS (Applied Materials Co., Ltd.) was used, and foreign matter having a size of 1.0 μm or more was counted. The foreign substance increase rate was evaluated according to the following criteria.

In addition, the foreign substance increase rate is (the number of foreign substances in the sample after the moisture resistance test / initial sample Number of foreign objects in the product). Practically, the determination criterion 3 or more is desirable. The results are shown in the table.

(Judgment criteria)

6: less than 1.1

5: 1.1 or more and less than 1.3

4: 1.3 or more and less than 1.5

3: 1.5 or more and less than 2.0

2: 2.0 or more and less than 3.0

1: 3.0 or more

<Thermal cycle test>

The increase rate of the coating foreign material after storage of the composition of an Example and a comparative example under the following temperature conditions was evaluated.

Temperature condition (1): 45 ℃ / 24H

Temperature condition (2): 23 ℃ / 24H

Temperature condition (3): -18 ℃ / 24H

The coating foreign matter was evaluated by repeating three times in the order of temperature condition (1), temperature condition (2), and temperature condition (3).

<Evaluation of coating foreign matter>

The colored composition was coated on a silicon wafer so that the thickness of the coated film became 0.6 μm, and then heated on a hot plate at 90 ° C. for 2 minutes to obtain a colored composition layer.

For the substrate on which the colored composition layer was formed, a defect evaluation device ComPLUS (Applied Materials) was used. Count the foreign objects on it.

Incidentally, the foreign substance increase rate was calculated by (the number of foreign substances after the thermal cycle test / the number of foreign substances immediately after preparation), and was evaluated according to the following classification.

(Judgment criteria)

6: less than 1.1 (best)

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

4: 1.3 or more and less than 1.5 (slightly good)

3: 1.5 or more and less than 2.0 (within tolerance)

2: 2.0 or more and less than 4.0 (out of tolerance)

1: 4.0 or more (out of tolerance)

From the results shown in the table, it was found that the toluene composition in the coloring composition was 0.001 ppm to 10 ppm, and the line width uniformity of the coloring pattern could be maintained well even if it was left for a long time.

In addition, it was found that when at least one of the sodium ion concentration and the potassium ion concentration in the coloring composition is 0.01 ppm to 20 ppm, foreign matter is less likely to be generated when it is left in a low temperature environment for a long time.

In addition, it was found that the moisture content in the coloring composition is 0.005 ppm to 3 ppm, so that good light resistance can be maintained even if it is left under low oxygen concentration for a long time.

It was also found that in Examples 79 to 86, any evaluation result other than the evaluation of long-term stability over time was good.

Claims (11)

A coloring composition comprising (A) a pigment polymer, (B) a solvent, a hardening compound having two or more terminal ethylenically unsaturated bonds, an alkali-soluble resin, and a photopolymerization initiator, and (A The pigment polymer has a partial structure derived from an xanthracene pigment having a cationic site and an anionic site, and the pigment polymer (A) is a pigment polymer containing a repeating unit represented by the general formula (a1-1). The toluene concentration in the coloring composition is 0.001 ppm to 10 ppm.

In the general 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 compound having an xanthracene derived from the following general formula (J ') Part of the structure,

In the general formula (J '), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m represents an integer of 0 to 5. The coloring composition according to item 1 of the scope of patent application, wherein the water content in the coloring composition is 0.005 ppm to 3 ppm. The coloring composition according to item 1 or 2 of the scope of the patent application, wherein at least one of sodium ion concentration and potassium ion concentration in the coloring composition is 0.01 ppm to 20 ppm. The coloring composition according to item 1 or item 2 of the scope of the patent application, wherein the anion site is a bis (sulfofluorenyl) fluorenimide anion, a tri (sulfofluorenyl) methylate anion, tetraarylboronic acid _{^{anion, B - (CN) n1 (}} oR a) 4-n1, and _{^{PF n2 R P (6-n2}} ) -, where R ^a represents an alkyl group or an aryl group having a carbon number of 1 to 10 carbon atoms is 6 to 10 N1 represents 1 to 4, R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6. The coloring composition according to claim 1 or claim 2, wherein the anion site is a bis (sulfofluorenyl) fluorenimide anion or a tris (sulfofluorenyl) methylate anion. The coloring composition according to item 1 or item 2 of the patent application scope further contains a phthalocyanine pigment. The coloring composition according to item 1 or 2 of the scope of patent application, which is for forming a coloring layer of a color filter. A method for manufacturing a color filter, comprising the steps of: applying a coloring composition according to any one of claims 1 to 7 on a support to form a coloring composition layer; The colored composition layer is exposed in a pattern A light step; and a step of developing and removing the unexposed portion to form a colored pattern. A method for manufacturing a color filter, comprising the steps of: applying the coloring composition according to any one of claims 1 to 7 on a support to form a coloring composition layer, and A step of forming a colored layer by hardening; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by performing exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask A step of dry etching the colored layer. A method for manufacturing a solid-state imaging element includes the method for manufacturing a color filter according to item 8 or item 9 of the scope of patent application. A method for manufacturing an image display device includes the method for manufacturing a color filter according to item 8 or item 9 of the scope of patent application.