KR102003241B1 - Pigment dispersion, process for producing pigment dispersion, colored composition, cured film, color filter, process for producing color filter, solid imaging element, image display device, and composition - Google Patents

Abstract

The present invention relates to a pigment dispersion for providing a color filter or the like having high color fastness to color, a coloring composition using the pigment dispersion, a method for producing a pigment dispersion, a cured film, a color filter, a method for producing a color filter, Display devices and compositions. The pigment dispersant of the present invention is a pigment dispersion containing a dispersant having a pigment structure, a pigment, and a solvent, wherein the dispersant having a pigment structure is a pigment multimer having two or more pigment structures in the same molecule, Wherein the dispersant having a dye structure selected from a dye, a xanthine dye, a xanthine dye, a cyanine dye and a squarylium dye has a non-absorbance represented by the following formula (A?) At a maximum absorption wavelength at 400 nm to 800 nm of 5 Or more.
E = A / (cxl) ... (A?)

Description

TECHNICAL FIELD [0001] The present invention relates to a pigment dispersion, a method for producing a pigment dispersion, a coloring composition, a cured film, a color filter, a method for producing a color filter, a solid-state image pickup device, an image display device and a composition FILTER, PROCESS FOR PRODUCING COLOR FILTER, SOLID IMAGING ELEMENT, IMAGE DISPLAY DEVICE, AND COMPOSITION}

The present invention relates to a pigment dispersion, a method for producing a pigment dispersion, a coloring composition, a cured film, a color filter, a method for producing a color filter, a solid-state image pickup device, an image display device and a composition.

2. Description of the Related Art In recent years, demand for solid-state image pickup devices such as CCD (Charge Coupled Device) image sensors has been greatly increased due to the spread of digital cameras and mobile phones equipped with cameras. Color filters are used as key devices for these displays and optical elements, and further demands for higher sensitivity and miniaturization are increasing. Such a color filter usually has three primary color patterns of red (R), green (G), and blue (B), and serves to decompose the transmitted light into three primary colors.

Patent Document 1 discloses a pigment dispersion containing a pigment dispersant having a dye skeleton, a pigment, and a solvent, wherein a difference between a maximum absorption wavelength of the pigment dispersant having a dye skeleton and a maximum absorption wavelength of the pigment is 200 nm or less.

In Patent Document 2, there is disclosed an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a radial oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, , An isocyanate group, and a hydroxyl group is described in JP-A-2001-348209.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-118060 Patent Document 2: JP-A-2007-277514

Coloring compositions using various dispersants have been studied. However, recently, coloring compositions used for color filters and the like are required to be further improved in decoloring properties.

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object of the present invention is to provide a pigment dispersion for providing a color filter or the like having high discoloration resistance, and a coloring composition using the pigment dispersion. It is also an object of the present invention to provide a method of producing a pigment dispersion, a cured film, a color filter, a method of manufacturing a color filter, a solid-state image pickup device, an image display device and a composition.

The inventors of the present invention have studied in detail and found that the above problems can be solved by using a dispersant having a predetermined dye structure, and have completed the present invention.

More specifically, the above problems are solved by the following means <1>, <17> or <18>, preferably by <2> to <16>.

<1> A pigment dispersion containing a dispersant having a pigment structure, a pigment, and a solvent,

Wherein the dispersing agent having a dye structure has a dye structure selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye,

A dispersing agent having a pigment structure is a pigment multimer having two or more pigment structures in the same molecule and has a specific absorption of at least 5 represented by the following formula (A?) At a maximum absorption wavelength at 400 nm to 800 nm;

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

c represents the concentration of the dispersant having a pigment structure in the solution, in which the unit is expressed in mg / ml.

<2> The dye structure of the dispersant having a dye structure included an anionic portion and the anion portion is, sulfonic acid anion, carboxylic acid anion, tetra aryl _{^{anion, BF 4 -, PF 6 -}} , SbF 6 - to the general formula ( A pigment dispersion liquid according to < 1 &gt;, wherein the pigment dispersion is at least one selected from the group consisting of a group including a structure represented by the formula (A1) and a group including a structure represented by the following formula (A2);

In formula (A1)

[Chemical Formula 1]

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-.

In general formula (A2)

(2)

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

<3> The pigment dispersion according to <1> or <2>, wherein the pigment is contained in an amount of 80 to 150 parts by mass based on 100 parts by mass of the dispersant having a pigment structure.

<4> The pigment dispersion according to any one of <1> to <3>, wherein the dispersant having a dye structure has a weight average molecular weight of 3000 to 50000.

<5> The pigment dispersion according to any one of <1> to <4>, wherein the dispersant having a dye structure has an acid value of 27 mgKOH / g or more and less than 200 mgKOH / g.

<6> A coloring composition comprising the pigment dispersion according to any one of <1> to <5> and a curable compound.

&Lt; 7 > The colored composition according to < 6 >, further comprising a photopolymerization initiator.

<8> The coloring composition according to <6> or <7>, wherein the total solid content of the coloring composition is 25% by mass or more and the sum of the dispersing agent having a pigment structure and the pigment is 60% by mass or more.

<9> The coloring composition according to any one of <6> to <8>, which is used for a color filter.

&Lt; 10 > A cured film obtained by curing the coloring composition according to any one of < 6 > to < 9 >.

<11> A color filter using the coloring composition according to any one of <6> to <9>.

&Lt; 12 > A process for producing a colored composition, comprising the steps of applying a coloring composition according to any one of < 6 > to < 9 > onto a support to form a coloring composition layer; exposing the coloring composition layer in a pattern; And removing the unexposed portion to form a colored pattern.

&Lt; 13 > A process for producing a colored layer, comprising the steps of applying the coloring composition according to any one of < 6 > to < 9 >

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

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

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

&Lt; 14 > A solid-state image pickup device having a color filter according to < 11 >, or a color filter manufactured by the method of < 13 >

<15> An image display device having a color filter according to <11>, or a color filter manufactured by a manufacturing method of a color filter according to <12> or <13>.

<16> A method for producing a pigment, comprising the step of dispersing a pigment in the presence of a dispersant having a pigment structure,

Wherein the dispersing agent having a dye structure has a dye structure selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye,

The dispersant having a pigment structure is a pigment multimer having two or more pigment structures in the same molecule and has a specific absorption of at least 5 represented by the following formula (A?) At a maximum absorption wavelength at 400 nm to 800 nm: Way;

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

c represents the concentration of the dispersant having a pigment structure in the solution, in which the unit is expressed in mg / ml.

<17> A composition containing a resin, a pigment and a solvent represented by the following general formula (1)

Wherein the resin has a dye structure selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye,

Wherein the resin has a specific absorbance of 5 or more represented by the following formula (A?) At a maximum absorption wavelength at 400 nm to 800 nm;

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

c represents the concentration of the resin having a pigment structure in the solution, in which the unit is expressed in mg / ml;

In general formula (1)

(DR ² ) _n -R ¹ - (L ¹ -P) _m - (One)

In the general formula (1), R ¹ represents a linking group of (m + n)

P represents a monovalent substituent having a repeating unit,

D represents a dye structure,

R ² and L ¹ each independently represent a single bond or a divalent linking group,

m represents an integer of 1 to 13,

When m is 1, P represents a monovalent substituent having two or more repeating units,

When m is 2 or more, a plurality of P's may be different from each other, or an average value of the number of repeating units constituting a plurality of P's is 2 or more,

n represents an integer of 2 to 14,

When n is 2 or more, a plurality of Ds may be different from each other,

m + n represents an integer of 2 to 15;

<18> A resin composition comprising 80 to 150 parts by mass of a pigment and 100 parts by mass of a resin containing a solvent, based on 100 parts by mass of a resin containing a repeating unit represented by the following general formula (A)

Wherein the resin has a dye structure selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye,

Wherein the resin has a specific absorbance of 5 or more represented by the following formula (A?) At a maximum absorption wavelength at 400 nm to 800 nm;

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

c represents the concentration of the resin having a pigment structure in the solution, in which the unit is expressed in mg / ml; A repeating unit represented by the general formula (A);

(3)

In the general formula (A), X ₁ represents a linking group formed by polymerization, and L ¹ represents a single bond or a divalent linking group. DyeI represents the pigment structure.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pigment dispersion for providing a color filter or the like having a high discoloration resistance, and a coloring composition using the pigment dispersion. It has also become possible to provide a method for producing a pigment dispersion, a cured film, a color filter, a method for producing a color filter, a solid-state image pickup device, an image display device and a composition.

Hereinafter, the contents of the present invention will be described in detail.

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

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

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

In the present specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the coloring composition. The solid content and concentration in the present invention refer to those at 25 占 폚.

As used herein, the term " (meth) acrylate "refers to both or either of acrylate and methacrylate, and" Methacryloyl "refers to both acryloyl and methacryloyl, or either.

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

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

In the present specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values measured by Gel Permeation Chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by using TSKgel Super AWM-H (a plasticizer, 6.0 mm ID x 15.0 cm ) Can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

<Pigment dispersion>

The pigment dispersion of the present invention is a pigment dispersion containing a dispersant having a pigment structure, a pigment and a solvent, wherein the dispersant having a pigment structure is selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye The dispersant having a pigment structure and having a pigment structure is a pigment-like polymer having two or more pigment structures in the same molecule, and has a specific absorption of at least 5 (represented by the following formula (A?) At a maximum absorption wavelength at 400 nm to 800 nm to be.

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

c represents the concentration of the dispersant having a pigment structure in the solution, in which the unit is expressed in mg / ml.

Here, the cell length refers to the length of a cell used for measuring the absorbance.

The "dispersant having a pigment structure" in the present invention is a pigment multimer having two or more pigment structures in the same molecule. The reason why the pigment multimer is effective as a dispersant is not clear, but it is considered that two or more pigment structure sites of the pigment multimer are adsorbed to the pigment, thereby facilitating dispersion progress in the pigment dispersion process.

The number of pigment structures of the dispersant having a pigment structure in the same molecule is 2 or more, preferably 2 to 100, more preferably 2 to 50, and more preferably 2 to 20.

With the above configuration, decolorization can be suppressed. The reason why such an effect can be obtained is not clarified yet, but when the above-mentioned dispersant is used in combination with the pigment, the pigment is easily adsorbed to the pigment region of the dispersant, and the discoloration can be suppressed.

Further, it is possible to further contain the dispersant and the pigment, and the light resistance of the cured film can be further improved.

Further, with the above-described constitution, the development residue when the colored composition is formed can be further suppressed, and the color unevenness (roughness) can be further suppressed.

<< Dispersing agent with pigment structure >>

<<< Pigment structure >>>

The dispersant having a pigment structure has a pigment structure selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye.

Among these dye structures, a triarylmethane dye and a xanthine dye are more preferable.

Hereinafter, the dye structure preferably used in the present invention will be described in detail.

<<<< Triaryl Methane Pigment >>>>

One mode of the dye structure is one having a partial structure derived from a triarylmethane dye. As the triarylmethane dye, a structure represented by the following formula (TP) is exemplified.

Equation (TP)

[Chemical Formula 4]

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

Is bonded to another site of the dispersant (preferably, R ^{2 in} the general formula (1) or L ^{1 in the} general formula (A)) through any one of Rtp ¹ to Rtp ¹⁰ in the formula (TP) , And more preferably through Rtp ^5, to other parts of the dispersing agent.

As Rtp ¹ to Rtp ⁶ , a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group are preferable. Rtp ⁵ is a hydrogen atom or NRtp ⁹ Rtp ¹⁰ are preferred, NRtp ⁹ Rtp ¹⁰ is particularly preferred. Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a straight-chain or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. The substituents represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be substituents exemplified in Substituent Group A to be described later. In particular, the substituent represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be a straight or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, An aryl group having 6 to 15 carbon atoms, a carboxyl group or a sulfo group is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a phenyl group or a carboxyl group is more preferable. In particular, Rtp ⁶ and Rtp ⁸ are preferably an alkyl group having 1 to 5 carbon atoms, and Rtp ⁷ is preferably an alkenyl group (particularly preferably a phenyl group to which two adjacent alkenyl groups are connected), a phenyl group or a carboxyl group.

a, b, or c each independently represent an integer of 0 to 4; In particular, a and c are each preferably 0 or 1, and more preferably 0. b is preferably an integer of 0 to 2, more preferably 0 or 2.

Specific examples of the compound represented by the formula (TP) are shown below, but the present invention is not limited thereto. In the following specific examples, X ^- represents an anion.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

<<<< xanthan pigment >>>>

As the xanthene dye, there is exemplified a dye having a partial structure derived from a xanthene compound represented by the following formula (J) as a dye structure.

[Chemical Formula 8]

In the formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m represents an integer of 0 to 5 . X ^- represents an anion site. When X &lt; ^{- &} gt ^; is absent, at least one of R ⁸¹ to R ⁸⁵ includes an anion. (R ^{2 in} the general formula (1) or L in the general formula (A)) of the dispersing agent through any one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ in the formula (J) ¹ ), and more preferably through R ^85, to other parts of the dispersing agent.

The substituent groups R ⁸¹ to R ⁸⁵ in the formula (J) can take are the same as the substituents exemplified in the group of the substituent group A described later.

In the formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are bonded to each other independently to form a 5-membered, 6-membered or 7-membered ring, Or a 7-membered unsaturated ring may be formed. When the substituent is a 5-membered, 6-membered or 7-membered ring which may be further substituted, it may be substituted with a substituent described for R ⁸¹ to R ^{85. When} the substituent is substituted by two or more substituents, May be different or different.

In the formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are bonded to each other independently to form a 5-membered, 6-membered and 7-membered ring Or a 5-membered, 6-membered or 7-membered unsaturated ring having 5-membered, 6-membered or 7-membered unsaturated rings, Pyrrole ring, furan ring, thiophen ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexane ring, A cyclopentadienyl group, a cyclopentadienyl group, a cyclopentadienyl group, and a pyridazin ring group.

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

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

When X ^- represents an anion, reference may be made to the description of the case where the anion site described later is a different molecule. When X ^- is absent and at least one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ contains an anion, reference may be made to the description of the case where the anion site is present in the same repeating unit.

Hereinafter, specific embodiments (first and second aspects) of the compound represented by the formula (J) will be described.

(The first embodiment of the compound represented by the formula (J)

The compound represented by the formula (J) is a compound wherein one of R ⁸¹ and R ⁸³ is a group represented by the following formula (2), the other of R ⁸¹ and R ⁸³ is a hydrogen atom, a group represented by the following formula (2) May represent an aryl group or an alkyl group other than the group represented by the general formula (2). Each of R ⁸² and R ⁸⁴ may independently represent a hydrogen atom, an alkyl group, or an aryl group.

In general formula (2)

[Chemical Formula 9]

In formula (2), R ¹ and R ² each independently represent an alkyl group, an aryl group or a heterocyclic group having at least 3 carbon atoms, and each of X ¹ to X ³ independently represents a hydrogen atom or a monovalent substituent. The dye compound represented by the general formula (1) has an anion site in the molecule and / or in addition to the molecule.

In the general formula (1), one of R ⁸¹ and R ⁸³ is a group represented by the general formula (2), and the other of R ⁸¹ and R ⁸³ is a hydrogen atom, a group represented by the following general formula (2) Represents an aryl group or alkyl group other than the group represented by the formula (2), and may be an aryl group other than the group represented by the formula (2) or the group represented by the formula (2). In addition, both of R ⁸¹ and R ⁸³ may be a group represented by the general formula (2). When both R ⁸¹ and R ⁸³ are groups represented by the general formula (2), the groups represented by the two general formula (2) may be the same or different.

In the general formula (2), R ¹ and R ² each independently represent an alkyl group, an aryl group, or a heterocyclic group having at least 3 carbon atoms, a secondary or tertiary alkyl group having 3 to 12 carbon atoms, or an isopropyl group.

Specific examples of the alkyl group having 3 or more carbon atoms include linear, branched or cyclic alkyl groups having 3 to 24 carbon atoms, 3 to 18 carbon atoms, and 3 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (e.g., t-butyl group), a pentyl group, a hexyl group, a heptyl group, , A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1-norbornyl group and a 1-adamantyl group, and examples thereof include a propyl group, an isopropyl group, a butyl group, a t- An ethyl group, a propyl group, an isopropyl group, a butyl group (t-butyl group), a pentyl group, a hexyl group, a heptyl group, An octyl group, a 2-ethylhexyl group, an isopropyl group, a t-butyl group, and a 2-ethylhexyl group.

The aryl group includes a substituted or unsubstituted aryl group. The substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent group are the same as the substituent group A described later.

The hetero ring of the heterocyclic group may be a 5-membered or 6-membered ring, and they may be ring-opened or not ring-opened. It may be an aromatic hetero ring or a non-aromatic hetero ring. Examples of the substituent include pyridine ring, pyrazine ring, pyridazin ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring, A thiazole ring, a thiazole ring, a thiazole ring, a thiazole ring, a thiazole ring, a benzothiazole ring, an isothiazole ring, a benzoisothiazole ring, A thiazole ring, an isoxazole ring, a benzoisooxazole ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, an imidazolidine ring, a thiazoline ring and the like. Among them, aromatic heterocyclic rings may be used, and examples thereof include pyridine ring, pyrazine ring, pyridazin ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, A pyrazole ring, an imidazole ring, a benzoxazole ring, a thiadiazole ring, or a pyrazole ring, a thiadiazole ring (1,3,4-thiadiazole ring), a thiazole ring, Thiadiazole ring, 1,2,4-thiadiazole ring). They may have a substituent, and examples of the substituent are the same as those of the aryl group described later.

R ¹ and R ² may be an alkyl group having 3 or more carbon atoms and an alkyl group having 3 to 12 carbon atoms.

In the general formula (2), X ¹ to X ³ each independently represent a hydrogen atom or a monovalent substituent. As the substituent, there is exemplified Substituent Group A described later. X ¹ to X ³ may be a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, an alkylthio group, a sulfonamide group or a sulfamoyl group.

Examples of the aryl group other than the group represented by the general formula (2) include a phenyl group. The phenyl group may or may not have a substituent. As the substituent, a substituent group A described later is exemplified and may be an alkyl group or an aryl group.

R ⁸² and R ⁸⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and the alkyl group and the aryl group may or may not have a substituent.

The substituted or unsubstituted alkyl group may be an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the same ones as the Substituent Group A described later. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (t-butyl group), an n-octyl group and a 2-ethylhexyl group.

The substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent group are the same as the substituent group A described later.

R ⁸² and R ⁸⁴ may be a hydrogen atom, an alkyl group, or a hydrogen atom.

(The second aspect of the compound represented by the formula (J)).

In the compound represented by the formula (J), R ⁸¹ and R ⁸³ are each independently an aliphatic hydrocarbon group, and R ⁸² and R ⁸⁴ each independently may be an aromatic hydrocarbon group.

R ⁸¹ and R ⁸³ are each independently an aliphatic hydrocarbon group and may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group, a propyl group or a butyl group, n-propyl group, iso-propyl group, n-butyl group. R ⁸¹ and R ⁸³ may be the same or different, but may be the same. The alkyl group as R ⁸¹ and R ⁸³ may have a substituent, but may not have a substituent.

R ⁸² and R ⁸⁴ are each independently an aromatic hydrocarbon group and may be a phenyl group. The aromatic hydrocarbon group as R ⁸² and R ⁸⁴ may have a substituent, may be selected from Substituent Group A described later, may be an alkyl group having 1 to 5 carbon atoms, may be a methyl group, an ethyl group, a propyl group or a butyl group, n-propyl group, n-butyl group.

At least one of R ⁸¹ and R ⁸³ , R ⁸² and R ⁸⁴ may be represented by the following general formula (A1-1-2).

In general formula (A1-1-2)

[Chemical formula 10]

In the general formula (A1-1-2), R ²³ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonylamido group, , A sulfonylamide group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, and R ²² and R ²⁶ each independently represent an alkyl group having 1 to 5 carbon atoms .

In the general formula (A1-1-2), R ²³ to R ²⁵ may be a hydrogen atom or a halogen atom.

In the general formula (A1-1-2), R ²² and R ²⁶ each independently represent an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be a methyl group, an ethyl group, a propyl group, a butyl group, or a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group.

R ⁸⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group or a sulfonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom, and may be a fluorine atom or a chlorine atom. The aliphatic hydrocarbon group may also be an aliphatic hydrocarbon group having 1 to 10 carbon atoms. The aliphatic hydrocarbon group is exemplified by an alkyl group and an alkenyl group, and may be an alkyl group. The aromatic hydrocarbon group may be an aryl group or a phenyl group.

Specific examples of the xanthene compound are shown below, but the present invention is not limited thereto. In the following specific examples, X ^- represents an anion. In addition, any one hydrogen atom of the dye structure bonds with the polymer skeleton.

In the dye structure, the cations are not localized, and therefore, they exist on the carbon atom of the nitrogen atom or the nitrogen ring as shown below, for example.

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

<<<< Cyanine color >>>>

The cyanine dye is preferably a partial structure derived from a compound (cyanide compound) represented by the following general formula (PM). In the present invention, a cyanide compound refers to a compound having a dye site including a cyanide skeleton in a molecule.

[Chemical Formula 17]

In the general formula (PM), ring Z1 and ring Z2 each independently represent a heterocycle which may have a substituent. and l represents an integer of 0 or more and 3 or less. X ^- represents an anion.

As a preferable range of the general formula (PM), for example, reference can be made to paragraphs 0077 to 0084 of Japanese Laid-Open Patent Publication No. 2013-29760, the contents of which are incorporated herein by reference. In particular, Z1 and Z2 each independently represent a nitrogen-containing heterocycle having a substituent, more preferably a nitrogen-containing condensed heterocycle having a substituent, and more preferably an indole ring having a substituent. l is preferably 1.

Further, in the specific example of the cyanine dye described in paragraphs 0077 to 0084 of Japanese Patent Application Laid-Open No. 2013-29760, it is preferable to disperse the other part of the dispersant (preferably, It is preferably bonded to R ² of formula (1) or L ¹ of formula (A), more preferably to Z1 or Z2 to bind to another part of the dispersant.

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

[Chemical Formula 18]

<<<< Squarylium pigment >>>>

As the squarylium dye, a partial structure derived from a compound represented by the following general formula (K) (squarylium compound) is preferable. In the present invention, the term "squarylium compound" refers to a compound having a dye moiety including a squarylium skeleton in its molecule.

[Chemical Formula 19]

In the general formula (K), A and B each independently represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group such as pyrrole, imidazole, pyrazolyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, Indolyl, and the like, and indole is preferred.

As a preferable range of the general formula (K), reference can be made, for example, to paragraphs 0088 to 0106 of Japanese Laid-Open Patent Publication No. 2013-29760, which disclosure is incorporated herein by reference.

Specific examples of the squarylium dye include, for example, the following. Further, for example, reference can be made to paragraph 0105 of Japanese Laid-Open Patent Publication No. 2013-29760. Further, in a specific example of the squarylium dye, R ² of the general formula (1) described below or a group represented by the general formula (A) ) is to be preferred, more preferably of bonded and L ¹⁾ and, combined with the other parts of the dispersing agent through the a or B.

[Chemical Formula 20]

In the dispersant having a pigment structure used in the present invention, the hydrogen atoms in the dye structure may be substituted with substituents selected from Substituent Group A below.

(Substituent group A)

Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, An alkyl group such as methyl, ethyl, propyl, isopropyl, butyl (preferably t-butyl), pentyl, hexyl, heptyl, Cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms such as vinyl, allyl, (Preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl, 3-pentanyl, , An aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably a carbon number of 6 to 24, 2-thienyl, 4-pyridyl, 2-furyl, 2-thienyl, etc.), a heterocyclic group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, (Preferably having 3 to 38 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms, Is a silyl group having 3 to 18 carbon atoms such as trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), a hydroxyl group, a cyano group, a nitro group An alkoxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferably having 6 to 48 carbon atoms, More preferably an aryloxy group having 6 to 24 carbon atoms, such as phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms (Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a silyloxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy) (For example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably an acyloxy group having 2 to 24 carbon atoms , An alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, and examples of the alkoxy group having 3 to 12 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy and dodecanoyloxy) For example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbo (Preferably cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxy Carbonyloxy),

A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-diethyl Sulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecyl (Preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyloxy), an arylsulfonyloxy group (e.g., phenylsulfonyloxy), an arylsulfonyloxy group (Preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms , An alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms, and examples of such an alkoxycarbonyl group having 2 to 12 carbon atoms, such as formyl, acetyl, pivaloyl, benzoyl, tetradecanyl, cyclohexanoyl) For example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl groups Is preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 48 carbon atoms, N-diethylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, Carbamoyl, N-methyl-N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group More preferably an amino group having not more than 24 carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino) Is an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, (For example, 4-pyridylamino), a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetamido group, (Preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a ureido group, for example, a ureido group, a ureido group, a thienyl group, N, N-dimethyl N-phenylureido), an imide group (preferably an imide group having not more than 36 carbon atoms, more preferably not more than 24 carbon atoms, such as an N-succinimide group and an N-phthalimide group) An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably a carbon number of 2 to 24, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino , Octadecyloxycarbonylamino, cyclohexyloxycarbonylamino),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably a carbon number 7 to 24, such as phenoxycarbonylamino), a sulfonamido group (preferably having 1 to 20 carbon atoms, Preferably 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a methanesulfonamido group, a butanesulfonamido group, a benzenesulfonamido group, a hexadecanesulfonamido group, a cyclohexanesulfonamido group, , A sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoyl Amino), an azo group (preferably having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms, such as phenyl azo group and 3-pyrazolyl azo group), an alkyl thio group (preferably having 1 to 48 carbon atoms, More preferably, Alkylthio groups having 1 to 24 carbon atoms, such as methylthio, ethylthio, octylthio, cyclohexylthio), arylthio groups (preferably having 6 to 48 carbon atoms, more preferably 6 to 48 carbon atoms, (Preferably phenylthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazolyl, (Preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include an alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, (Preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 20 carbon atoms, 48, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, (Preferably having a carbon number of 6 or less, more preferably a carbon number of 1 to 6, and more preferably a carbon number of 1 to 6), a sulfonyl group, a sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group (Preferably an arylsulfonyl group having from 6 to 24 carbon atoms, more preferably a carbon number of 24 or less, and still more preferably an arylsulfonyl group having from 2 to 48 carbon atoms, more preferably a carbon number of 6 to 24, such as phenylsulfonyl and 1-naphthylsulfonyl) A sulfamoyl group such as sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl) (Preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (Preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms (For example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino), an alkyloxycarbonyloxy group (preferably an alkyloxycarbonyloxy group having 5 to 30 carbon atoms, more preferably 5 to 10 carbon atoms ), Thiol groups, and the like.

These substituents may be further substituted. When two or more substituents are present, they may be the same or different. If possible, they may be connected to form a ring.

For details, see, for example, paragraphs 0027 to 0038 of Japanese Laid-Open Patent Publication No. 2013-29760, the contents of which are incorporated herein by reference.

<<< Anion Site >>>

The dye structure in the present invention includes an anionic moiety.

The anion moiety constituting the dye structure of the dispersant having the dye structure includes a sulfonic acid anion, a carboxylic acid anion, a tetraarylborate anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , a structure represented by the following formula (A1) And a group including a structure represented by the following formula (A2), and it is preferably at least one selected from the group consisting of a sulfonic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) Methide anion, tetraarylborate anion, BF ₄ ^- , PF ₆ ^- , and SbF ₆ ^- .

In formula (A1)

[Chemical Formula 21]

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-.

In general formula (A2)

[Chemical Formula 22]

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

The anion moiety may be bonded to the dye structure via a covalent bond or may be located outside the molecule.

<<<< If the anion site is outside the molecule >>>>

The case where the anion site is located outside the molecule means that the cation and the anion site are not bonded through a covalent bond but exist as a separate molecule.

The anion moiety is not particularly limited, but from the viewpoint of heat resistance, it is preferable that the anion moiety is an anion of nucleus. The non-nucleophilic anion site is preferably a known non-nucleophilic anion described in, for example, Japanese Patent Application Laid-Open No. 2007-310315, paragraph No. 0075. Here, the term &quot; non-nucleophilic &quot; means a property of not attacking the pigment by nucleation.

As the anionic site, a sulfonic acid anion, carboxylic acid anion, sulfonyl imide anion, bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion, carboxylic acid anion, tetra aryl anion, -CON ^- CO- , -CON ^- SO ₂ -, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- and B ^- (CN) ₃ OCH ₃ . More preferably, a sulfonic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methide anion, a carboxylic acid anion, a tetraarylborate anion, BF ₄ ^- , PF ₆ ^- , And SbF ₆ ^- .

Among these, the anion moiety is more preferably an unconjugated anion having a structure represented by the following (AN-1) to (AN-5).

(23)

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

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

&Lt; EMI ID =

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

X ³ , X ⁴ and X ⁵ each independently are the same as X ¹ and X ² , and the preferred range is also synonymous.

(25)

In the formula (AN-3), X ⁶ represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom.

X ⁶ is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

(26)

In the formula (AN-4), X ⁷ represents an alkylene group having 1 to 10 carbon atoms and a fluorine atom.

X ⁷ is preferably a perfluoroalkylene group having 1 to 10 carbon atoms, more preferably a perfluoroalkylene group having 1 to 4 carbon atoms.

(27)

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

Each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is independently an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.

The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. A halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamido group and a nitro group, More preferably a fluorine atom or an alkyl group, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

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

The mass per molecule of the non-nucleophilic anion site is preferably 100 to 1,000, more preferably 200 to 500.

Specific examples of the anion site of the second embodiment include the following, but the present invention is not limited thereto.

(28)

[Chemical Formula 29]

(30)

(31)

<<<< When the anion moiety binds through the dye structure and the covalent bond >>>>

Next, a description will be given of the case where the anion site binds through the dye structure and the covalent bond.

As the anion part of the _{^{case, -SO 3 -, -COO -,}} -PO 4 -, it is preferably at least one member selected from the following formula structure represented by the structure and the following general formula (A2) represented by (A1).

In formula (A1)

(32)

(In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-.)

In the general formula (A1), at least one of R ¹ and R ² is -SO ₂ -, and it is preferable that indicates, both the R ¹ and R ² -SO ₂ - and more preferably indicating.

The above general formula (A1) is more preferably represented by the following general formula (A1-1).

In general formula (A1-1)

(33)

(In the general formula (A1-1), R ¹ and R ² each independently represent -SO ₂ - or -CO-, and X ¹ and X ² each independently represent an alkylene group or an arylene group.)

In the general formula (A1-1), R ¹ and R ² are represented by the general formula (A1), and in R ¹ and R ² and agreement, are also the same preferable range.

When X ¹ represents an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 8, more preferably from 1 to 6. When X ¹ represents an arylene group, the number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 12, and even more preferably 6. When X ¹ has a substituent, it is preferably substituted with a fluorine atom.

X ² represents an alkylene group or an arylene group, and an alkylene group is preferable. The number of carbon atoms of the alkylene group is preferably from 1 to 8, more preferably from 1 to 6, still more preferably from 1 to 3, and particularly preferably 1. When X ² has a substituent, it is preferably substituted with a fluorine atom. When either one of X ¹ and X ² is a compound end, an embodiment in which the alkylene group or arylene group is an alkyl group or an aryl group is exemplified.

In general formula (A2)

(34)

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

In the general formula (A2), R ³ ~ R at least one of ⁵ -SO ₂ -, and it is preferable that indicates, at least two of R ³ ~ R ⁵ -SO ₂ - and more preferably indicating.

<<<< In case of large amount of negative ions >>>>

The anion site in the present invention may be a multimer. That is, the dispersant having a dye structure used in the present invention may contain a repeating unit containing an anion site, and the anion site may be a separate molecule and may be a polymer. As an example of the case where the number of anion sites is large, it is preferable to introduce it as a repeating unit constituting a multimer in the second embodiment of the dispersant having a dye structure to be described later. In the first embodiment described later, it may be one of repeating units constituting P in the general formula (1).

Preferable examples of the repeating unit containing an anionic site include repeating units represented by formula (C).

In the general formula (C)

(35)

(In formula (C), X ¹ represents a main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, and anion represents the above anion site.)

In the general formula (C), X ¹ represents a main chain of a repeating unit, and usually represents a linking group formed by a polymerization reaction. In addition, the parts indicated by two * are repeated units.

And X ₁ and consent of the repeating unit represented by the general formula (A), specific examples of X ^1, described later, are also the same preferable range.

Specific examples of the repeating unit containing an anion in the present embodiment are shown below, but the present invention is not limited thereto.

(36)

The following specific examples show a state in which the anion structure is not dissociated, but it is needless to say that the state in which the anion structure is dissociated is also within the scope of the present invention.

(37)

(38)

[Chemical Formula 39]

(40)

(41)

A preferred embodiment of a dispersant having a pigment structure in the present invention will be described below. It goes without saying that the dispersant having a pigment structure in the present invention is not limited to these.

<< First Embodiment of Dispersant Having a Pigment Structure >>>

As an embodiment of the dispersant having a dye structure, there is a structure represented by the following general formula (1).

In general formula (1)

(DR ² ) _n -R ¹ - (L ¹ -P) _m - (One)

In the general formula (1), R ¹ represents a linking group of (m + n)

P represents a monovalent substituent having a repeating unit,

D represents a dye structure,

R ² and L ¹ each independently represent a single bond or a divalent linking group,

m represents an integer of 1 to 13,

When m is 1, P represents a monovalent substituent having two or more repeating units,

When m is 2 or more, a plurality of P's may be different from each other, or an average value of the number of repeating units constituting a plurality of P's is 2 or more,

n represents an integer of 2 to 14,

When n is 2 or more, a plurality of Ds may be different from each other,

m + n represents an integer of 2 to 15;

In the general formula (1), m represents an integer of 1 to 13. m is preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.

In the general formula (1), n represents an integer of 2 to 14. n is preferably 2 to 8, more preferably 2 to 7, particularly preferably 2 to 6, and even more preferably 2 to 5.

In the general formula (1), it is preferable that m + n represents an integer of 2 to 15.

In the general formula (1), R ¹ represents a linking group of (m + n). m + n satisfies 2 to 15.

The (m + n) linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms An atom, and a group consisting of 0 to 20 sulfur atoms, which may be unsubstituted or may further have a substituent.

Specific examples of the (m + n) linking group represented by R ¹ include a group having the following structural unit or a group formed by combining two or more of the following structural units (may form a ring structure).

The coloring composition of the present invention may contain a plurality of dispersing agents having a dye structure represented by the general formula (1), wherein m and n are different from each other. Therefore, the average value of m and n in the coloring composition of the present invention may not be an integer.

(42)

Examples of the (m + n) linking group represented by R ¹ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms Atoms, and groups formed from 0 to 10 sulfur atoms are preferred. More preferably from 1 to 50 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 30 oxygen atoms, from 1 to 100 hydrogen atoms, and from 0 to 7 Which is a sulfur atom. More preferably from 1 to 40 carbon atoms, from 0 to 8 nitrogen atoms, from 0 to 20 oxygen atoms, from 1 to 80 hydrogen atoms, and from 0 to 5 Which is a sulfur atom.

The (m + n) linking group represented by R ¹ may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, a halogen atom such as chlorine and bromine, a methoxycarbonyl group, an ethoxycarbonyl group, a cyclohexyl group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a hexyloxycarbonyl group, and a carbonic acid ester group such as a cyano group and a t-butylcarbonate group.

Specific examples of (m + n) linking groups represented by R ¹ are shown below. However, the present invention is not limited thereto.

(43)

(44)

[Chemical Formula 45]

(46)

(1), (2), (10), (11), (16) to (20), and (26) to (29) are preferable.

In the general formula (1), R ² and L ¹ each independently represent a single bond or a divalent linking group. When a plurality of R ² and L ¹ are present, they may be the same or different.

The divalent linking groups may include from 1 to 100 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, from 1 to 200 hydrogen atoms, and from 0 to 20 A sulfur atom-containing group, which may be unsubstituted or may further have a substituent.

Specific examples of the divalent linking group include groups having the following structural units or a combination of two or more of the following structural units.

(47)

R ^{2 is a} single bond or an alkylene group having from 1 to 50 carbon atoms, from 0 to 8 nitrogen atoms, from 0 to 25 oxygen atoms, from 1 to 100 hydrogen atoms, and from 0 Lt; / RTI &gt; to 10 sulfur atoms. More preferably from 1 to 30 carbon atoms, from 0 to 6 nitrogen atoms, from 0 to 15 oxygen atoms, from 1 to 50 hydrogen atoms, and from 0 Is a divalent linking group formed by from seven to seven sulfur atoms. More preferably 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 Is a divalent linking group formed by five to five sulfur atoms.

The divalent linking group represented by R ² may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, An alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, a halogen atom such as chlorine or bromine, a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxycarbonyl group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as a cyclohexyloxycarbonyl group, and a carbonic acid ester group such as a cyano group and a t-butylcarbonate group.

In the general formula (1), P represents a monovalent substituent having two or more repeating units. When m is 2 or more, the m number of P may be the same or different.

When m is 1, P represents a monovalent substituent having two or more (preferably 2 to 100, more preferably 2 to 50, more preferably 2 to 20) repeating units. When m is 2 or more, the average value of the number of repeating units of m P is 2 or more (preferably 2 to 100, more preferably 2 to 50, and more preferably 2 to 20) to be. According to this embodiment, the flatness of the coated film is improved.

the number of repeating units when m is 1, and when m is 2 or more, the average value of the number of repeating units of m P can be determined by NMR (Nuclear Magnetic Resonance). Specifically, it can be calculated, for example, by finding m from the peak area ratio of the linking group of (m + n) represented by R ¹ and the dye structure D and dividing the peak area ratio of the repeating unit by m.

Examples of the repeating unit constituting P include a repeating unit containing an alkali-soluble group such as an acid group, a repeating unit containing a polymerizable group, a repeating unit derived from a macromonomer, etc., and a repeating unit containing an alkali- At least. These repeating units may each contain only one kind, or two or more kinds thereof. Hereinafter, these repeating units will be described in detail.

<<<< Repeating unit containing an anagen >>>>

Examples of the acid group of the repeating unit including an acid group include a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. The acid group contained in the repeating unit including an acid group may be contained singly or two or more kinds thereof may be contained.

When P contains repeating units containing an acid group, the proportion of repeating units containing repeating units having an acid group is preferably 10 to 80 moles, more preferably 10 to 65 moles, per 100 moles of repeating units constituting P More preferable.

<<<< Repeating units containing other alkali-soluble groups >>>>

As the repeating unit containing another alkali-soluble group, a repeating unit containing a phenolic hydroxyl group or the like is exemplified.

It is also preferable that P contains a repeating unit having a group consisting of repeating of 2 to 20 unsubstituted alkyleneoxy chains in the side chain (hereinafter sometimes referred to as "(b) repeating unit").

The number of repeating units of the alkyleneoxy group contained in the repeating unit (b) is preferably from 2 to 10, more preferably from 2 to 15, and still more preferably from 2 to 10.

One alkyleneoxy group is represented by - (CH ₂ ) _n O-, and n is an integer, but n is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 or 3.

The repeating unit of 2 to 20 unsubstituted alkyleneoxy chains may contain only one kind of alkyleneoxy chain or two or more kinds thereof.

The repeating unit (b) is preferably represented by the following general formula.

(48)

(Wherein X ₁ represents a linking group formed by polymerization, L ₁ represents a single bond or a divalent linking group, and P represents a group containing a group consisting of repeating alkyleneoxy chains.)

X ¹ and L ¹ in the general formula (P) are in agreement with X ₁ and L ₁ in the general formula (A), respectively, and preferable ranges are also the same.

P represents a group containing a group consisting of repeating alkyleneoxy chains, more preferably consisting of a group-terminal atom or terminal group formed by repetition of -alkyleneoxy chains.

The terminal atom or the terminal group is preferably a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a hydroxyl group, more preferably a hydrogen atom, , And a hydrogen atom is particularly preferable.

Examples of the repeating unit (b) are shown below, but are not limited thereto.

(49)

When P contains a repeating unit containing another alkali-soluble group, it is preferably 10 to 80 moles, more preferably 10 to 65 moles, per 100 moles of the repeating unit constituting P, for example.

The proportion of repeating units containing an alkali-soluble group or an alkali-soluble group is preferably 10 to 80 moles, more preferably 10 to 65 moles, per 100 moles of repeating units constituting P Do.

<<<< Repeating units containing polymeric groups >>>>

As the polymerizable group contained in the repeating unit containing a polymerizable group, a known polymerizable group capable of crosslinking by radicals, acids, and heat can be used, and examples thereof include groups containing an ethylenically unsaturated bond, cyclic ethers (epoxy group, (Meth) acryloyl groups are more preferable, and glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acryloyl groups are more preferable, and groups containing an ethylenically unsaturated bond are preferable, More preferred is a (meth) acryloyl group derived from methyl (meth) acrylate.

Examples of the method of introducing the polymerizable group include: (1) a method of modifying and introducing a polymerizable group-containing compound into a repeating unit into which a polymerizable group is to be introduced, such as (a) a repeating unit, (2) a method of copolymerizing and introducing a polymerizable group- .

The amount of the polymerizable group contained in the dispersant having a pigment structure is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and particularly preferably 0.3 to 1.0 mmol based on 1 g of the pigment structure, .

When P contains a repeating unit containing a polymerizable group, the amount thereof is preferably 5 to 40 moles, more preferably 5 to 35 moles, per 100 moles of all the repeating units constituting P, for example.

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

(50)

(51)

(52)

<<<< Repeating Units Derived from Macromonomers >>>>

The repeating unit derived from the macromonomer is preferably a repeating unit derived from an ethylenically unsaturated monomer. The repeating unit derived from the macromonomer may be contained only in one kind or in two or more kinds.

The weight average molecular weight of the repeating unit derived from the macromonomer is preferably 1,000 or more and 50,000 or less, more preferably 1,000 or more and 20,000 or less, still more preferably 2,000 or more and 10,000 or less, particularly preferably 2,000 or more and 5,000 or less.

The repeating unit derived from the macromonomer is preferably a repeating unit having a polyester macromonomer moiety having flexibility and excellent hydrophilicity from the viewpoint of the dispersibility of the pigment, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion.

The repeating unit derived from the macromonomer is preferably represented by the following general formula (b-3A), more preferably represented by the following general formula (b-3B), more preferably represented by the following general formula (b-3C) desirable.

In the general formula (b-3A)

(53)

(Wherein R ^3A represents a hydrogen atom or a methyl group), L ^3A represents a single bond or a divalent linking group, and A ^3A represents a linking group having a weight average molecular weight of 1000 to 50000 (b-3) Lt; / RTI &gt;

In the general formula (b-3A), when L ^3A represents a divalent linking group, examples of the divalent linking group include at least one kind selected from an alkylene group, an arylene group and a heteroarylene group, _{, -CONH-, -CO 2 -, -SO} 2 NH-, -O-, -S- and -SO ₂ -, and include groups comprising a combination of at least one kind of groups selected from, in particular, an alkylene group , -CO ₂ -, -CO- and -CONH-.

In general formula (b-3B)

(54)

(Wherein R ^3A represents a hydrogen atom or a methyl group, L ^3A represents a single bond or a divalent linking group, R ^3B represents an alkylene group, R ^3C represents an alkyl group, n represents 5 Represents an integer of 1 to 100).

In the general formula (b-3B), L ^3A is an L ^3A and consent of the above-described formula (3A-b), the preferred range is also the same.

In the general formula (b-3B), R ^3B is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably a linear alkylene group having 1 to 10 carbon atoms, and an unsubstituted linear chain having 5 to 20 carbon atoms Is more preferable, and - (CH ₂ ) ₅ - is particularly preferable.

In the general formula (b-3B), R ^3C is preferably a linear or branched alkyl group having 5 to 20 carbon atoms.

In the general formula (b-3B), n represents an integer of 5 to 100, preferably an integer of 5 to 80.

The compound represented by the general formula (b-3C)

(55)

(In the general formula (b-3C), R ^3A represents a hydrogen atom or a methyl group, R ^3B represents an alkylene group, R ^3C represents an alkyl group, and n represents an integer of 5 to 100.

In the general formula ^{(b-3C), R 3A} , R 3B, R 3C and n have the above-described formula (b-3B), and of the R ^3A, R ^3B, R ^3C and n and copper, the preferred range is also the same .

Examples of the repeating unit derived from the macromonomer include the following formulas. In the following formulas, n is an integer of 5 to 100, and examples thereof include n = 10, n = 30, n = 50 and the like.

(56)

A commercially available macromonomer, for example, a repeating unit derived from AA-6 from Doogusa Co., is also an example of a repeating unit derived from a preferable macromonomer in the present invention.

When P contains a repeating unit derived from a macromonomer, the ratio is preferably 3 to 20 moles per 100 moles of the total repeating units.

<<<< Other Repeat Units >>>>

The P in the present invention may have a repeating unit other than the repeating unit described above. Specific examples of the repeating unit which may be contained in P include a phenol group such as a lactone group, an acid anhydride group, an amide group, -COCH ₂ CO-, a development promoter such as a cyano group, a long chain and cyclic alkyl group, an aralkyl group, An alkylene oxide group, a hydrophilic regulator such as a hydroxyl group, a maleimide group and an amino group, and the like.

These may be contained only in one kind or in two or more kinds.

As an introduction method, there may be mentioned a method of introducing into the dye structure in advance, and a method of copolymerizing monomers having the above groups.

When P contains other repeating units, the ratio is preferably 3 to 20 moles with respect to 100 moles of the total repeating units.

Specific examples of the repeating unit including the above-mentioned acid group or other repeating units are shown, but the present invention is not limited thereto. Needless to say, the repeating units derived from M-10, O-6, O-7 and the like used in the examples described later are also used as preferable examples.

(57)

In the general formula (1), D represents the above-described dye structure. The preferred range is also agreement.

<< Synthesis Method of Dispersant Having Pigment Structure Represented by General Formula (1) >>

The dispersant having a pigment structure represented by the above general formula (1) can be synthesized by the following method or the like.

(1) a polymer in which a functional group selected from a carboxyl group, a hydroxyl group and an amino group is introduced at the terminal thereof, an acid halide having a dye structure, an alkyl halide having a dye structure, or an isocyanate having a dye structure, Lt; / RTI &gt;

(2) A method in which a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a dye structure are subjected to Michael addition reaction.

(3) A method in which a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a dye structure are reacted in the presence of a radical generator.

(4) A method of reacting a polymer having a plurality of mercaptans introduced at its terminal and a compound having a carbon-carbon double bond and a pigment structure in the presence of a radical generator.

(5) A method of radical polymerization of a vinyl compound in the presence of a thiol compound having a dye structure.

From the viewpoint of ease of synthesis, the synthesis method of (2) to (5) is preferable, and the synthesis method of (3) to (5) is more preferable.

As the synthesis method of the above (5), more specifically, a radical polymerization method in the presence of a compound represented by the following general formula (3) is preferable.

(DR ⁴ - (S) _p ) _n - R ³ - (SH) _m - (3)

In the general formula (3), R ³ represents a linking group of (m + n), D represents a dye structure, R ⁴ represents a single bond or a divalent linking group, S represents a sulfur atom, SH represents a thiol group, m represents an integer of 1 to 13, n represents an integer of 2 to 14, and when n is 2 or more, a plurality of D may be mutually different and m + Represents an integer of 2 to 15, and p represents 0 or 1.

In the general formula (3), D is synonymous with D in the general formula (1), and preferred embodiments are also the same.

In the general formula (3), R ³ is synonymous with R ¹ in the general formula (1), and preferred embodiments are also the same.

In the general formula (3), R ⁴ is the same as R ² in the general formula (1), and preferred embodiments are also the same.

In the general formula (3), m and n are each the same as m and n in the general formula (1), and preferred embodiments are also the same.

In the general formula (3), p represents 0 or 1.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but from the viewpoint of ease of synthesis, the following method (7) is more preferable.

(6) a method of converting a halide compound having a dye structure into a mercaptan compound (a method of reacting with a thioether, a method of hydrolyzing, a method of directly reacting with NaSH, a method of reacting with CH ₃ COSNa, .

(7) a method in which a compound having a dye structure and having a functional group capable of reacting with a mercapto group is additionally reacted with a compound having 2 to 15 mercapto groups in one molecule

Examples of the "functional group capable of reacting with the mercapto group" in (7) include an acid halide, an alkyl halide, an isocyanate, and a carbon-carbon double bond.

It is particularly preferable that the "functional group capable of reacting with the mercapto group" is a carbon-carbon double bond, and the addition reaction is a radical addition reaction. As the carbon-carbon double bond, a monovalent or divalent vinyl group is more preferable in terms of reactivity with a mercapto group.

Specific examples of the compound having 2 to 15 mercapto groups in a molecule include the following compounds.

(58)

[Chemical Formula 59]

(60)

Particularly preferable compounds among the above are (S-1), (S-2), (S-10), (S-11), (S-16) to (S-20), (S-26) to (S-29).

The radical addition reaction product of the "compound having 2 to 15 mercapto groups in one molecule" and the "compound having a pigment structure and having a functional group capable of reacting with a mercapto group" includes, for example, And a compound having a dye structure and having a functional group capable of reacting with a mercapto group "are dissolved in an appropriate solvent, a radical generator is added thereto, and the mixture is heated at about 50 ° C to 100 ° C (Thion-ene reaction method).

Examples of a suitable solvent to be used in the thiol-ene reaction method include a compound having 3 to 10 mercapto groups in one molecule, a compound having a pigment structure and having a functional group capable of reacting with a mercapto group, Can be arbitrarily selected depending on the solubility of the " radical addition reaction product "

Methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl lactate, , Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used in combination of two or more kinds.

Examples of the radical generator include 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis- (2,4'-dimethylvaleronitrile), 2,2'-azobis Azo compounds such as azobisisobutyrate, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

The vinyl compound used in the above synthesis method (5) is not particularly limited, and for example, the same vinyl compound as used for obtaining the substituent represented by P in the general formula (1) is used.

The vinyl compound may be polymerized singly or in combination of two or more.

Further, when the composition is applied to a photocurable composition requiring an alkali developing treatment, it is more preferable to copolymerize a vinyl compound having at least one acid group and a vinyl compound having at least one acid group.

Particularly, it is preferable that the vinyl compound and the compound represented by the general formula (3) are used and polymerized by a known method in accordance with a conventional method. The compound represented by the general formula (3) functions as a chain transfer agent, and hereinafter may be simply referred to as a "chain transfer agent ".

For example, these vinyl compounds and chain transfer agents are dissolved in an appropriate solvent, a radical polymerization initiator is added thereto, and polymerization is carried out in a solution at about 50 ° C to 220 ° C (solution polymerization method) .

Examples of a suitable solvent to be used in the solution polymerization method may be arbitrarily selected depending on the solubility of the monomer to be used and the copolymer to be produced. Methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl lactate, , Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used in combination of two or more kinds.

Examples of the radical polymerization initiator include 2,2'-azobis (isobutyronitrile), 2,2'-azobis- (2,4'-dimethylvaleronitrile), 2,2'-azo Azo compounds such as dimethyl bisisobutyrate, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

<<< Second Embodiment of Dispersant Having a Pigment Structure >>>

As another embodiment of the dispersant having a dye structure, a polymer containing a repeating unit having a dye structure (hereinafter may be referred to as "(a) repeating unit") is exemplified.

(A), the general formula (B), and the general formula (C) shown in paragraphs 0276 to 0304 of Japanese Laid-Open Patent Publication No. 2013-28764 It is preferable that at least one of the appearing repeating units is a skeleton, or a large amount represented by the formula (D) is preferable. The description of paragraphs 0276 to 0304 of Japanese Laid-Open Patent Publication No. 2013-28764 is hereby incorporated by reference.

The dispersant having a pigment structure preferably contains a multimer containing repeating units represented by the following formula (A) in the skeleton structure of the repeating unit (a).

The proportion of repeating units having a dye structure is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, of the total repeating units constituting the above multimer.

The repeating unit represented by the general formula (A)

(61)

(In the general formula (A), X ₁ represents a linking group formed by polymerization, L ₁ represents a single bond or a divalent linking group, and Dye I represents a pigment structure.)

In the general formula (A), X ₁ represents a linking group formed by polymerization. That is, a part forming a repeating unit corresponding to a main chain formed by a polymerization reaction. In addition, the parts indicated by two * are repeated units. X ₁ is preferably -CH ₂ -CH ₂ - or -CH ₂ -C (CH ₃ ) -. Examples of the divalent linking group when L ₁ represents a divalent linking group include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc.) A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group or a naphthylene group), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, C (= O) -, -CO 2 -, -NR-, -CONR-, -O 2 C-, -SO-, -SO 2 - and these represents a linking group formed by linking two or more, -COO- Or a linking group containing a phenylene group.

As the structure of the X ₁ -L ₁ moiety, a linking group represented by the following formulas (XX-1) to (XX-24) is preferable and a (meth) acrylic linkage chain represented by (XX- More preferably selected from vinyl-based connecting chains represented by the following formulas (XX-10) to (XX-17), (XX-18), (XX-19) and (XX- Chain linkage chain represented by the following formula (XX-1) and (XX-2), the styrene-based linkage chain represented by (XX-10) And more preferably a styrene linkage chain represented by (meth) acrylic linkage chain and (XX-11) represented by (XX-1) and (XX-2).

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

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

(62)

(63)

In the general formula (A), DyeI represents the above-described dye structure.

The multimer containing the repeating unit represented by the general formula (A) is obtained by (1) a method of synthesizing a monomer having a dye structure by addition polymerization, (2) a method of synthesizing a monomer having a dye structure such as an isocyanate group, an acid anhydride group, A method of reacting a polymer having a reactive functional group with a dye having a functional group capable of reacting with a highly reactive group (a hydroxyl group, a primary or secondary amino group, a carboxyl group, or the like).

In the addition polymerization, known addition polymerization (radical polymerization, anion polymerization, cation polymerization) can be applied. Among them, the synthesis by radical polymerization in particular makes it possible to temper the reaction conditions, Since it is not decomposed. For the radical polymerization, known reaction conditions can be applied. That is, the multimer used in the present invention is preferably an addition polymer.

Among them, a multimer having a repeating unit represented by the general formula (A) in the present invention is preferably a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance.

Examples of the repeating unit (a) preferably used in the present invention are shown below. It is needless to say that the present invention is not limited to these. X ^- represents an anionic moiety. In addition, although some of X &lt; ^- &gt; is shown as a state in which the anion structure is not dissociated, it goes without saying that the dissociation state is also included in the present invention.

&Lt; EMI ID =

(65)

(66)

(67)

The dispersant having a pigment structure in the second embodiment may have another repeating unit in addition to the repeating unit (a) such as the repeating unit represented by the above-mentioned general formula (A) desirable.

Examples of other repeating units include repeating units containing an alkali-soluble group such as an acid group, repeating units containing a polymerizable group, repeating units derived from a macromonomer, and the like, and include at least a repeating unit containing an alkali- . With regard to these repeating units, each of the repeating units described in the first embodiment of the dispersant having the above-described dye structure can be employed, and the preferable range is also the same. The repeating units other than the above-mentioned repeating units may be contained, and for the other repeating units, the repeating units described in the first embodiment of the dispersing agent having the above-mentioned dye structure may be employed, The range is the same.

When the dispersant having a dye structure in the second embodiment contains a repeating unit containing an acid group, the proportion thereof is preferably from 10 to 80 mol%, more preferably from 10 to 65 mol% desirable.

When the dispersant having a dye structure in the second embodiment contains a repeating unit containing another alkali-soluble group, the proportion thereof is preferably from 10 to 80 mol%, more preferably from 10 to 65 mol% Is more preferable.

The proportion of the repeating unit containing the entire alkali-soluble group, in which the dispersant having the dye structure in the second embodiment contains an acid group or other alkali-soluble group, is preferably 10 to 80 mol%, more preferably 10 To 65 mol% is more preferable.

When the dispersant having a dye structure in the second embodiment contains a repeating unit having a polymerizable group, the proportion thereof is preferably from 5 to 40 mol%, more preferably from 5 to 35 mol%, of the total repeating units Do.

When the dispersant having a dye structure in the second embodiment contains a repeating unit derived from a macromonomer, the proportion thereof is preferably 3 to 20 mol% of the total repeating units.

When the dispersant having a pigment structure in the second embodiment contains other repeating units, the proportion thereof is preferably 3 to 20 moles per 100 moles of the total repeating units.

<<< Properties of dispersants having pigment structure >>>

The weight average molecular weight of the dispersant having a pigment structure is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more. The upper limit is preferably 50000 or less, more preferably 40000 or less, and even more preferably 30000 or less. By satisfying the above range, the flammability becomes better. Further, the developability is improved, and the development residue can be further reduced.

The acid value of the dispersant having a pigment structure is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, even more preferably 27 mgKOH / g or more, and particularly preferably 30 mgKOH / g or more. The upper limit of the acid value is preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, still more preferably 130 mgKOH / g or less, and even more preferably 120 mgKOH / g or less . By satisfying the above range, the developability is further improved, and the development residue can be further reduced.

A method of measuring the specific absorption of a dispersant having a pigment structure includes a dispersant having a pigment structure such that the maximum absorbance at 400 nm to 800 nm is 1.0, for example, using a solvent having sufficient solubility for a dispersant having a pigment structure , And measuring the absorbance of this solution at 25 캜 using a cell having an optical path length of 1 cm. As the solvent for measurement of the non-absorbance, those having sufficient solubility in a dispersant having a pigment structure can be suitably used. Preferred examples of the solvent include tetrahydrofuran, methanol, isopropyl alcohol, dimethyl sulfoxide, acetonitrile, ethyl acetate, hexane, toluene, water, concentrated sulfuric acid and methanesulfonic acid. When tetrahydrofuran has sufficient solubility, tetrahydrofuran is used.

The specific absorbance expressed by the formula (A?) At the maximum absorption wavelength in the range of 400 nm to 800 nm is 5 or more, preferably 10 or more, more preferably 20 or more, and particularly preferably 25 or more. The upper limit is not specifically defined, but is usually 99 or less.

The dispersant having a pigment structure may be used alone or in combination of two or more.

<< Pigment >>

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

As the inorganic pigment, a metal compound or carbon black (CI Pigment Black 7), which is represented by a metal oxide, a metal complex salt or the like, can be mentioned. Specific examples of the metal compound include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony and complex oxides of metals.

As the organic pigment, for example,

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

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

C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 179, 209, 220, 224, 242, 254, 255, 264, 270;

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

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

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

C. I. Pigment Brown 25, 28;

C. I. Pigment Black 1; And the like.

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

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

C. I. Pigment Orange 36, 71,

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

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

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

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

C. I. Pigment Black 1

These organic pigments can be used singly or in various combinations in order to enhance spectral control and color purity. Specific examples of the combination are shown below. For example, as the red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone A yellowish pigment or a mixture with a perylene-based red pigment may be used. Examples of the anthraquinone pigments include CI Pigment Red 177, and the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224. As the diketopyrrolopyrrole pigment, CI Pigment Red 254, and is preferably mixed with CI Pigment Yellow 139 in view of color resolution. The mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100: 50, and more preferably from 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted according to the obtained spectroscopy.

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

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

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

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

The primary particle diameter of the pigment refers to a value measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)).

Among them, the pigment is preferably a pigment selected from anthraquinone pigment, diketopyrrolopyrrole pigment, phthalocyanine pigment, quinophthalone pigment, isoindoline pigment, azomethine pigment, and dioxazine pigment .

In particular, CI Pigment Red 177 (anthraquinone pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, 36, 58, CI Pigment Blue 15: 6 ), CI Pigment Blue 15: 3 (phthalocyanine pigment), CI Pigment Yellow 138 (quinophthalone pigment), CI Pigment Yellow 139, 185 (isoindoline pigment), CI Pigment Yellow 150 CI Pigment Red 163, CI Pigment Blue 15: 3 and CI Pigment Blue 15: 6 are more preferable, and CI Pigment Red 177, CI Pigment Red 254, CI Pigment Blue 15: 3 and CI Pigment Blue 15: 6 are more preferable .

The content of the pigment in the pigment dispersion is preferably from 1 to 50 mass%, more preferably from 1 to 30 mass%, and still more preferably from 1 to 15 mass%. The amount is preferably not less than 40 parts by mass, more preferably not less than 50 parts by mass, more preferably not less than 80 parts by mass, and particularly preferably not less than 100 parts by mass, based on 100 parts by mass of the dispersant having a pigment structure. The upper limit value is preferably 600 parts by mass or less, more preferably 400 parts by mass or less, more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, based on 100 parts by mass of the dispersant having a pigment structure, And particularly preferably 150 parts by mass or less. Particularly, the amount is preferably 80 to 150 parts by mass.

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

<< Solvent >>

The solvent contained in the pigment dispersion is not particularly limited so long as it satisfies solubility of each component and coating property of the coloring composition, but is preferably selected in consideration of solubility, coating ability, and safety of a dispersant having a pigment structure . The solvent is preferably an organic solvent.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, , Methyl lactate, ethyl lactate, alkyloxyacetate (for example, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate , Ethoxyacetic acid ethyl and the like), 3-oxypropionic acid alkyl esters (for example, methyl 3-oxypropionate, ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and the like), 2-oxypropionic acid alkyl esters (for example, 2-oxypropyl Propyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- (2-methoxypropionate), 2- Methyl 2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol Diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethylene glycol mono Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc. , And ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbon such as toluene and xylene .

These organic solvents may be mixed with two or more kinds in view of the solubility of the dispersing agent having a pigment structure or the like and the improvement of the coating surface shape.

The content of the solvent in the pigment dispersion is preferably such that the total solid content of the pigment dispersion is 5% to 80% by mass, more preferably 5% to 50% by mass, More preferably 10 to 30% by mass.

The pigment dispersion may contain only one kind of solvent, or may contain two or more kinds of solvents. When two or more kinds are included, the total amount is preferably in the above range.

&Lt; Production method of pigment dispersion >

The method for producing a pigment dispersion of the present invention comprises a step of dispersing a pigment in the presence of a dispersant having a pigment structure, wherein the dispersant having a pigment structure is selected from the group consisting of triaryl methane dye, xanthine dye, cyanine dye, and squarylium A dispersant having a pigment structure selected from pigments and having a pigment structure is a pigment-like polymer having two or more pigment structures in the same molecule, and has a ratio (A?) At a maximum absorption wavelength at 400 nm to 800 nm And an absorbance of 5 or more.

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

c represents the concentration of the dispersant having a pigment structure in the solution, in which the unit is expressed in mg / ml.

Dispersants and pigments having a pigment structure are in agreement with the above-described dispersing agents and pigments having a pigment structure, and preferable ranges are also the same.

As the dispersion method, it is preferable to mix the dispersion liquid containing the pigment, the pigment and the solvent with a bead mill, and dispersing the dispersion liquid using a dispersing machine, for example.

<Composition>

The composition of the present invention is a composition containing a pigment and a solvent, relative to 100 parts by mass of the resin represented by the general formula (1)

Wherein the resin has a dye structure selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye,

Wherein the resin has a specific absorption of 5 or more, expressed by the following formula (A?) At a maximum absorption wavelength in the range of 400 nm to 800 nm.

The composition of the present invention is a composition containing 80 to 150 parts by mass of a pigment and 100 parts by mass of a resin containing a repeating unit represented by the formula (A) and a solvent, wherein the resin is a triarylmethane A pigment having a pigment structure selected from a coloring matter, a xanthine coloring matter, a cyanine coloring matter and a squarylium coloring matter,

Wherein the resin has a specific absorption of 5 or more, expressed by the following formula (A?) At a maximum absorption wavelength in the range of 400 nm to 800 nm.

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

and c is a composition showing the concentration of the resin having the pigment structure in the solution, in which the unit is expressed in mg / ml.

Such a composition is used as the pigment dispersion of the present invention. The preferred range of the composition is the same as the preferred range of the corresponding pigment dispersion.

<Coloring composition>

The coloring composition of the present invention contains the above pigment dispersion and a curable compound (a polymerizable compound, a thermosetting compound, a polyfunctional thiol compound, an alkali-soluble resin, etc.). The total content of the curing compound in the coloring composition is preferably from 1 to 50 mass%, more preferably from 2 to 40 mass%, and still more preferably from 5 to 20 mass%, based on the total solid content of the coloring composition.

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

With such a constitution, it is preferably used as a coloring composition for a color filter.

In addition, the coloring composition of the present invention preferably contains a photopolymerization initiator. Further, it may contain a dispersant other than the dispersant having the dye structure, a polymerization inhibitor, and a surfactant.

The content of the pigment dispersion in the coloring composition of the present invention is set after considering the content ratio with the pigment or the like to be described later.

The content of the pigment dispersion in the coloring composition is preferably such that the solid content of the pigment dispersion is 10 to 80 mass%, more preferably 30 to 70 mass%, and more preferably 40 to 60 mass%, based on the total solid content of the coloring composition. By mass is more preferable.

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

The content of the pigment in the coloring composition is preferably 25 mass% or more, more preferably 30 mass% or more, based on the total solid content of the coloring composition. The upper limit is preferably 50 mass% or less, and more preferably 40 mass% or less.

The total content of the pigment and the dispersant having the pigment structure in the coloring composition is preferably at least 60 mass%, more preferably at least 65 mass%, based on the total solid content of the coloring composition. The upper limit is preferably 99 mass% or less, and usually 90 mass% or less.

<<< Polymerizable compound >>>

As the polymerizable compound, known polymerizable compounds capable of crosslinking by radicals, acids, and heat can be used. Examples thereof include polymerizable compounds including ethylenically unsaturated bonds, cyclic ethers (epoxy, oxetane), methylol, and the like. The polymerizable compound is suitably selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds from the viewpoint of sensitivity. Of these, polyfunctional polymerizable compounds having four or more functionalities are preferable, and polyfunctional polymerizable compounds having five or more functionalities are more preferable.

Such a group of compounds is well known and can be used in the present invention without particular limitation. These may be, for example, monomers, prepolymers, that is, any of a dimer, a trimer and an oligomer or a mixture thereof and a chemical form thereof such as a multimer thereof. The polymerizable compounds in the present invention may be used alone or in combination of two or more.

Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, , Preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, as well as oligomers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, or a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, a reaction product of a monofunctional or polyfunctional alcohol, an amine, a thiol, a halogen or a tosyloxy group Also suitable are unsaturated carboxylic acid esters or amides having a cleavable substituent and reacting with monofunctional or polyfunctional alcohols, amines and thiols. It is also possible to use a group of compounds substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like in place of the above unsaturated carboxylic acid.

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

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 at normal pressure. As an example thereof, reference can be made, for example, to Japanese Patent Laid-Open Publication No. 2013-29760, paragraph 0227, which is incorporated herein by reference.

As a compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher under atmospheric pressure, reference may be made to the compounds described in Japanese Patent Application Laid-Open No. 2008-292970, paragraphs 0254 to 0257, Which is incorporated herein by reference.

Examples of the polymerizable compound include dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku), dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kayaku, (KAYARAD D-310; Nippon Kayaku), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku), ethyleneoxy-modified dipentaerythritol hexa Acrylate (commercially available from A-DPH-12E; Shin Nakamura Kagaku) and a structure in which these (meth) acryloyl groups are interposed between ethylene glycol and propylene glycol moieties (for example, Commercially available, SR454, SR494, SR499) are preferable. These oligomer types can also be used. Also, SR368 (Satoromy) and KAYARAD D-330 (Nippon Kayaku) are also preferable. Preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. If the polymerizable compound has an unreacted carboxyl group or the like, it can be used as it is. However, if necessary, the acid group may be introduced by reacting the hydroxyl group of the polymerizable compound with a nonaromatic carboxylic acid anhydride. Specific examples of the non-aromatic carboxylic acid anhydrides include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

As the polymerizable compound having an acid group, an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid are preferable, and a polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride And particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers of Doogose Seiyaku Co., Ltd.

One kind of the polymerizable compound having an acid group may be used alone, but two or more kinds of the polymerizable compounds having an acid group may be used in combination because it is difficult to use a single compound in the production.

The acid value of the polymerizable compound having an acid group is preferably from 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably from 5 mg KOH / g to 30 mg KOH / g. If the acid value of the polyfunctional monomer is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in terms of production and handling. Further, the photopolymerization performance is good and the curability such as the surface smoothness of the pixel is excellent. Therefore, when two or more kinds of polymerizable compounds having different acid groups are used in combination, or when a polymerizable compound having no acid group and a polymerizable compound having an acid group are used in combination, the acid value as the entire polymerizable compound is adjusted .

It is also a preferable embodiment that a polymerizable compound having a caprolactone structure is contained as the polymerizable compound.

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

(68)

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

(69)

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

(70)

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

The polymerizable compound having a caprolactone structure is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku. DPCA-20 (in the formulas (Z-1) to (Z-3) both be = 2, R ¹ in the group represented by Z-2), this number = 3, R ¹ of a group represented by the compound), DPCA-30 (the same formula, m = 1, formula (Z-2) the hydrogen atom DPCA-60 (the compound represented by the formula: m = 1, the number of groups represented by the formula (Z-2) = 6 and R ¹ are all hydrogen atoms), DPCA-120 m = 2, the number of groups represented by the formula (Z-2) = 6, and R ¹ are all hydrogen atoms).

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

The polymerizable compound may be a compound represented by the following general formula (Z-4) or (Z-5).

(71)

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

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

In the general formula (Z-5), the sum of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60 to be. Provided that when the sum of each n is 0, any one of X is a carboxyl group.

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

The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

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

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

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

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

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to ethylene oxide or propylene oxide by ring opening addition reaction And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride on the terminal hydroxyl group of the ring-opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

(A), (b), (f), (f), and (f) of the present invention. Specific examples include the compounds represented by the following formulas , (e) and (f) are preferable.

(72)

(73)

Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains of a saturating agent, pentylene of Nippon Kayaku DPCA-60, which is a hexafunctional acrylate having 6 oxygens, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

In the present invention, a compound having an epoxy group may also be used as the polymerizable compound. As the compound having an epoxy group, it is preferable to have two or more epoxy groups in one molecule. By using a compound having two or more epoxy groups in one molecule, the effect of the present invention can be more effectively achieved. The epoxy group is preferably 2 to 10, more preferably 2 to 5, and most preferably 3 in one molecule.

As the epoxy compound, reference can be made to the description of paragraphs 0091 to 0103 of Japanese Laid-Open Patent Publication No. 2014-153554, the contents of which are incorporated herein.

As commercial products of epoxy compounds, for example, bisphenol A type epoxy resins include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050 (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by Japan Epoxy Resins Co., Ltd.), and the like, as the bisphenol F type epoxy resin, JER152, JER157S70, JER157S65 (the above, Japan Epoxy Resin Co., Ltd., Japan Epoxy Resin Co., Ltd.), LCE-21 and RE-602S (manufactured by Nippon Kayaku Co., (EPICLON N-660, EPICLON N-665, EPICLON N-770, and EPICLON N-775 manufactured by DIC Corporation) EPICLON N-690, EPICLON N-690, EPICLON N-690, EPICLON N-690 (manufactured by DIC Corporation) Fat Examples of the epoxy resin include ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600 (Manufactured by Nagase ChemteX Corporation), PB 4700 (manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L and EX- . In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, EPPN-502 (manufactured by ADEKA Corporation) and JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.).

EPICLON HP-4700 (manufactured by DIC Corporation), EPICLON N-695 (manufactured by Mitsubishi Kagaku K.K.), DIC (manufactured by Mitsubishi Kagaku K.K.), and the like are commercially available as commercial products of epoxy group- (Manufactured by Mitsubishi Chemical Corporation) can be preferably used.

Further, in the present invention, as polymerizable compounds, there may be mentioned, for example, Japanese Patent Publication Nos. 48-41708, 51-37193, 2-32293, and 2-16765 Japanese Patent Publication No. 58-49860, Japanese Examined Patent Publication No. 56-17654, Japanese Examined Patent Publication No. 62-39417, Japanese Examined Patent Publication No. 62-39418 Also suitable are urethane compounds having the ethylene oxide skeleton described therein. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 By using the polymerizable compounds, a colored composition having a very high photosensitive speed can be obtained.

In the present invention, a compound having oxetane's popularity may also be used as the polymerizable compound. As a compound having an oxetecyl group, there may be mentioned the compounds described in paragraphs 0134 to 0145 of JP-A No. 2008-224970, the content of which is incorporated herein by reference. As specific examples, Aromaxhene OXT-121, OXT-221, OX-SQ, PNOX (the above, Doogase) can be used.

Examples of commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kogaku Pulp), UA-7200 (Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku), UA- -306T, UA-306I, AH-600, T-600, AI-600 (Kyowa now).

When the polymerizable compound is contained in the coloring composition, the content of the polymerizable compound is preferably from 1 to 30 mass%, more preferably from 2 to 25 mass%, and still more preferably from 5 to 20 mass%, based on the total solid content of the coloring composition. Is more preferable.

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

<< Multifunctional Thiol Compounds >>

The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound and the like. The polyfunctional thiol compound is preferably a secondary alkene thiol compound, particularly preferably a compound having a structure represented by the following general formula (T1).

The general formula (T1)

&Lt; EMI ID =

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

In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and L is particularly preferably an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and compounds represented by the formula (T2) are particularly preferable. These polyfunctional thiols can be used singly or in combination.

(75)

When the coloring composition of the present invention contains a polyfunctional thiol compound, it is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass, based on the total solid content excluding the solvent.

<< Photopolymerization initiator >>

The coloring composition of the present invention may further contain a photopolymerization initiator.

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

The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, Organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.

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

More preferably, it is a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound or an acetophenone compound , At least one compound selected from the group consisting of a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is particularly preferable, and an oxime compound is more preferable .

Particularly, when the coloring composition of the present invention is used in the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern in a sharp shape, so that it is important that the coloring composition is developed without residue on the unexposed portion with curing property. From this viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. Particularly, in the case of forming a fine pattern in the solid-state image pickup device, a stepper exposing machine is used for the curing exposure, and this exposing machine may be damaged by the halogen, and the addition amount of the photopolymerization initiator also needs to be suppressed to a low level, Taking this into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern such as a solid-state imaging element. Further, by using an oxime compound, it is possible to further improve the flammability.

As specific examples of the photopolymerization initiator used in the present invention, reference can be made, for example, to paragraphs 0265 to 0268 of JP-A-2013-29760, the contents of which are incorporated herein by reference.

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

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

The photopolymerization initiator is more preferably an oxime compound. Specific examples of the oxime initiator include compounds described in JP 2001-233842 A, compounds described in JP 2000-80068 A, and compounds described in JP 2006-342166 A.

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

As oxime compounds, see J. C. S. Perkin II (1979) pp. Pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP-A 2006-342166, etc. .

As a commercially available product, for example, IRGACURE-OXE-01 (manufactured by BASF) and IRGACURE-OXE-02 (manufactured by BASF) which have the following structures are suitably used. TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), Adeka acid NCI- 831 and ADEKA ACKLS NCI-930 (manufactured by ADEKA) can also be used.

[Formula 76]

As oxime compounds other than those described above, compounds described in Japanese Patent Publication No. 2009-519904 in which oxime is linked to carbazole N, compounds described in U.S. Patent No. 7626957 in which a hetero-substituent is introduced at the benzophenone moiety, Compounds disclosed in JP-A-2010-15025 and US-A-2009-292039 wherein a nitro group is introduced at the site, ketoxime compounds described in WO 2009-131189, triazine skeleton and oxime skeleton are the same Compounds described in U.S. Patent Publication No. 7556910 contained in the molecule, compounds described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, or the like may be used.

Preferably, for example, reference is made to paragraphs 0274 to 0275 of JP-A-2013-29760, the contents of which are incorporated herein by reference.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). Further, the N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the form (E) and the form (Z).

[Formula 77]

In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of the monovalent nonmetal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The above-mentioned substituent may be further substituted with another substituent.

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

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

In the general formula (OX-1), as the divalent organic group represented by A, an alkylene group, a cycloalkylene group or an alkane-ylene group having 1 to 12 carbon atoms is preferable. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified.

Specific examples (C-4) to (C-13) of the compound represented by formula (OX-1) are shown below, but the present invention is not limited thereto.

(78)

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 a high absorbance at 365 nm and 405 nm.

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

Specific examples of the molar extinction coefficient of the compound include an ultraviolet visible spectrophotometer (Varian Cary-5 spectrophotometer), an ethyl acetate solvent at a concentration of 0.01 g / L It is preferable to measure it.

The photopolymerization initiator used in the present invention may be used in combination of two or more as necessary.

When the coloring composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the colorant composition, 1 to 20% by mass.

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

<< Dispersants other than dispersants having a pigment structure >>

The coloring composition of the present invention may further contain a dispersant other than a dispersant having a pigment structure.

Examples of other dispersants include polymer dispersants such as polyamidoamine and salts thereof, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, modified poly (meth) acrylate, ) Acrylic copolymer, a naphthalenesulfonic acid-formalin condensate], and surfactants such as polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, and alkanolamine, and pigment derivatives. For details of these, reference may be made to the description of paragraphs 0045 to 0049 of Japanese Laid-Open Patent Publication No. 2014-130173, the contents of which are incorporated herein by reference.

When the coloring composition contains other dispersing agent, the total content of the other dispersing agent is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass relative to 100 parts by mass of the pigment More preferable.

In the present invention, it is also possible to adopt a constitution in which other dispersant is not substantially contained. The phrase "substantially not included" means that the level of the pigment dispersing agent is not mixed with the level, and it means, for example, 1% by mass or less of the total dispersing agent.

Other dispersants may be used alone or in combination of two or more. When two or more kinds are included, the total amount is preferably in the above range.

<< Alkali-soluble resin >>

The coloring composition of the present invention may further contain an alkali-soluble resin.

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

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

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

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

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

As the alkali-soluble resin, a monomer component essentially comprising a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may also be referred to as " (A).

(79)

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.

(ED2)

(80)

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

As a result, the colored composition of the present invention can form a cured coating film having excellent heat resistance as well as transparency. In the general formula (ED), 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, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl, and other straight or branched alkyl groups; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- (Isopropyl) -2,2 '- [oxybis (methylene)] - propenoate, di (n-propyl) -2,2' - [oxybis Di (isobutyl) -2,2 '- [oxybis (2-methoxyphenyl) -2,2'- Methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '- [oxybis Di (lauryl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Methoxyethyl) -2,2 '- [oxybis (meth) 2-propenoate, dibenzyl-2, 2 '- [oxy (2-methoxyphenyl) Bis (methylene)] bis-2-propenoate, diphenyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- )] Bis-2-propenoate, dicyclohexylcyclohexyl) -2,2 '- [oxybis (methylene)] bis- , 2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2' Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamantyl- 2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be either one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

The alkali-soluble resin may contain a repeating unit derived from an ethylenically unsaturated compound represented by the following formula (X) and / or a repeating unit derived from a compound represented by the formula (ED).

In general formula (X)

[Formula 81]

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

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

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.

(ED2)

(82)

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

In order to improve the crosslinking efficiency of the coloring composition of the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned alkali-soluble resin containing a polymerizable group include a dianal NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (a polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.) 106 (both manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), Cyclomer P series, Plackac CF200 series (all available from Daicel Chemical Industries, Ltd.) and Ebecryl 3800 (Dacelle Yucca). As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a Containing unsaturated group-containing acrylic resin obtained by the reaction of an acrylic resin with an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule , Acid pendant epoxy acrylate resin, polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group and an isocyanate A resin obtained by reacting a compound having a maleic anhydride group, 229207 and Japanese Unexamined Patent Application Publication No. 2003-335814, resins obtained by basic treatment of a resin having on its side chain an ester group having a leaving group such as a halogen atom or a sulfonate group on? In addition, ARC Liqueur RD-F8 (Nippon Shokubai) is also preferable.

As the alkali-soluble resin, a multi-component copolymer composed of a (meth) acrylic acid benzyl / (meth) acrylic acid copolymer and a (meth) benzyl acrylate / (meth) acrylic acid / other monomer is suitable. (Meth) acrylic acid benzylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate copolymer disclosed in Japanese Patent Application Laid-open No. 7-140654 (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / Methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / meta Acrylic acid copolymers, and particularly preferable examples thereof include copolymers of benzyl methacrylate / methacrylic acid and the like.

As the alkali-soluble resin, reference may be made to the description after Japanese Patent Application Laid-Open No. 20-204949, paragraphs 0558 to 0571 (corresponding to US Patent Application Publication No. 2012/0235099, <0685> to <0700>), Which is incorporated herein by reference.

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

(83)

(84)

The acid value of the alkali-soluble resin is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, more preferably 45 mgKOH / g or more, still more preferably 55 mgKOH / g or more, More preferably 130 mgKOH / g or more. The upper limit value is preferably 250 mgKOH / g or less, more preferably 210 mgKOH / g or less.

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

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

The coloring composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds of alkali-soluble resins. When two or more kinds are included, the total amount is preferably in the above range.

<<< solvent >>>

As the solvent, a solvent exemplified in the above-mentioned pigment dispersion can be used.

The content of the solvent in the coloring composition is preferably such that the total solid content of the coloring composition is 5 to 80 mass%, more preferably 5 to 50 mass%, and more preferably 10 to 30 mass% Is more preferable.

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

<<< polymerization inhibitor >>>

The coloring composition of the present invention preferably contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the production of the coloring composition.

Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxylamine have.

When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably about 0.01 to 5% by mass with respect to the mass of the coloring composition.

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

<<< Surfactant >>>

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

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

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

The fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-repellency, and the solubility in the coloring composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, and SC-103 (manufactured by Sumitomo 3M Co., Ltd.), F554, F780, and F781 (Manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by Asahi Glass Co., Ltd.), SC-104, SC-105, SC-1068, SC- (Manufactured by OMNOVA).

Specific examples of the nonionic surfactants include glycerol, trimethylol propane, trimethylol ethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Lactic acid esters such as di-stearate and sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 from BASF) Bridol), and the like.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Chemical Co., Ltd.), an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Polflor No. 75, No. 90, No. 95 (Kyoeisha Chemical Co., Ltd.), and W001 (Yuzo Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005 and W017 (Yusoh).

Examples of silicon based surfactants include fluorine-based surfactants such as TORAY Silicon DC3PA, TORAY Silicone SH7PA, TORAY Silicon DC11PA, TORAY Silicone SH21PA, TORAY Silicone SH28PA, TORAY Silicone SH29PA, TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 ", and Shin-Etsu are trademarks of Toshiba Corporation. Silicone "KP341", "KF6001", "KF6002", big chemistry "BYK307", "BYK323", and "BYK330".

When the surfactant is contained in the coloring composition of the present invention, the amount of the surfactant to be added is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the coloring composition.

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

<< Other Ingredients >>

The coloring composition of the present invention may further contain other components such as a dye, a cross-linking agent, an organic carboxylic acid, and an organic carboxylic acid anhydride in addition to the above-mentioned respective components as long as the effect of the present invention is not impaired.

<< Dye >>

The coloring composition of the present invention may contain a known dye. For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301, 6-11614, 2592207, 4808501, US 5667920, US 505950, JP 5-333207, JP 6-35183, JP-A 6-51115, JP-A-6-51115 6-194828 and the like can be used. Examples of the chemical structure include pyrazolone group, pyromethene group, anilino group, triarylmethane group, anthraquinone group, benzylidene group, oxolin group, pyrazolotriazoazo group, pyridazoazo group, And pyrrolopyrazole azo methane phosphoric acid, can be used. As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097.

<<< Crosslinking agent >>>

A crosslinking agent may be contained in the coloring composition of the present invention. By containing a crosslinking agent, the hardness of the resulting cured film can be further increased.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples of the crosslinking agent include (a) an epoxy resin, (b) at least one substituent selected from methylol group, alkoxymethyl group and acyloxymethyl group A phenol compound, a naphthol compound or a hydrolyzate substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group; (c) And a hydroxyanthracene compound. Among them, a polyfunctional epoxy resin is preferable.

For details of specific examples of the crosslinking agent and the like, reference can be made to the description in paragraphs 0134 to 0147 of Japanese Laid-Open Patent Publication No. 2004-295116, which is incorporated herein by reference.

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

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

<<< Organic Carboxylic Acid, Organic Carboxylic Anhydride >>>

The coloring composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1,000 or less and / or an organic carboxylic acid anhydride. As specific examples of the organic carboxylic acid and the organic carboxylic acid anhydride, reference may be made, for example, to Japanese Patent Application Laid-Open No. 2013-29760, paragraphs 0338 to 0340, the contents of which are incorporated herein by reference.

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

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

In addition to the above, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be added to the coloring composition, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116, the contents of which are incorporated herein by reference.

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

&Lt; Preparation method of colored composition >

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

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

The coloring composition of the present invention is preferably filtered with a filter for the purpose of eliminating foreign matters or reducing defects. So long as it is conventionally used for filtration applications and the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, a polyolefin resin such as polyethylene or polypropylene (PP) And the like). Of these materials, polypropylene (including high-density polypropylene) is preferable.

The pore diameter of the filter is preferably about 0.01 to 7.0 mu m, preferably about 0.01 to 3.0 mu m, more preferably about 0.05 to 0.5 mu m. By setting this range, it is possible to reliably remove fine foreign matter which inhibits the preparation of a uniform and smooth colored composition in a subsequent step.

When using a filter, other filters may be combined. At this time, the filtering with the first filter may be performed once, or may be performed two or more times.

It is also possible to combine the first filters having different pore sizes within the above-mentioned range. Here, the hole diameter can refer to the nominal value of the filter maker. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

The second filter may be formed of the same material as the first filter described above.

For example, the filtering with the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing the other components.

The coloring composition of the present invention is suitably used for forming a coloring layer of a color filter, because it can form a cured film having good light resistance, flame retardancy and flatness. The coloring composition of the present invention can be used for coloring a color filter used for a solid-state image pickup device (for example, a CCD, a Complementary Metal-Oxide Semiconductor (CMOS), or the like), an image display device such as a liquid crystal display And can be suitably used for pattern formation. In addition, it can be suitably used for producing printing ink, inkjet ink, and paint. Among them, it can be suitably used for the production of color filters for solid-state image pickup devices such as CCD and CMOS.

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

Next, the cured film and the color filter in the present invention will be described in detail with reference to the production method thereof. A method of manufacturing the color filter of the present invention will be described.

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

A first aspect of a method of manufacturing a color filter of the present invention is a method of manufacturing a color filter comprising the steps of forming a coloring composition layer by applying the coloring composition of the present invention on a support, And removing the unexposed portion of the layer by development to form a colored pattern. If necessary, a step of baking the coloring composition layer (pre-baking step) and a step of baking the developed colored pattern (post-baking step) may be provided. Hereinafter, these steps may be referred to as a pattern forming step.

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

The color filter of the present invention can be suitably obtained by the above production method. The details of these will be described below.

&Lt; Step of forming coloring composition layer &gt;

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

As a support which can be used in the present step, for example, a substrate for a solid-state imaging element provided with an imaging element (light-receiving element) such as CCD or CMOS on a substrate (for example, a silicon substrate) can be used.

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

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

If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate.

As a method of applying the coloring composition of the present invention on a support, various coating methods such as slit coating, inkjet coating, spin coating, flex coating, roll coating, screen printing and the like can be applied.

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

<< When pattern formation is performed by photolithography method >>

<<< Exposure Process >>>

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

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

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

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

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

<<< Pattern formation process >>>

Subsequently, the alkali developing process is carried out so that the coloring composition layer in the tailing part in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured part.

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

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo [5,4,0] -7-undecene. These alkaline compounds may be used in concentrations Is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 1% by mass, based on the total amount of the aqueous alkaline solution.

As the developing solution, an inorganic alkali may be used. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.

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

Subsequently, it is preferable to carry out a heat treatment (post-baking) after drying. If a multicolor colored pattern is formed, a cured film can be produced by sequentially repeating the process for each color. As a result, a color filter is obtained.

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

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

<< When pattern is formed by dry etching >>

The dry etching can be performed using an etching gas with the patterned photoresist layer as a mask in the colored layer. Specifically, a positive or negative radiation-sensitive composition is coated on the colored layer and dried to form a photoresist layer. In the formation of the photoresist layer, it is also preferable to perform the prebaking treatment. Particularly, as the formation process of the photoresist layer, it is preferable that a heat treatment after exposure and a heat treatment (post-bak treatment) after development are performed.

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

Specifically, as the positive radiation sensitive composition, a composition containing a quinone diazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinone diazide compound and an alkali-soluble resin is obtained by decomposing a quinone diazide group by irradiation with light having a wavelength of 500 nm or less to generate a carboxyl group and consequently becoming alkali-soluble from an alkali- . This positive type photoresist is used for the production of integrated circuits such as IC (Integrated Circuit) and LSI (Large Scale Integration) because the resolution is remarkably excellent. As the quinone diazide compound, a naphthoquinone diazide compound can be mentioned. Commercially available products include, for example, "FHi622BC" (FUJIFILM ELECTRONIC MATERIALS).

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

Subsequently, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a group of resist through holes. The formation of the resist pattern is not particularly limited and can be carried out by suitably optimizing the conventionally known photolithography technique. A resist pattern serving as an etching mask used in the next etching is provided on the colored layer by providing the resist through hole group in the photoresist layer by exposure and development.

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

As the developing solution, any solution can be used as long as it does not affect the coloring layer containing the colorant and dissolves the unexposed portions of the positive resist and the negative resist. For example, a combination of various organic solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving the alkaline compound in an amount of 0.001 to 10 mass%, preferably 0.01 to 5 mass%, is suitable. The alkaline compound may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, and the like. When an alkaline aqueous solution is used as a developing solution, cleaning treatment is generally performed with water after development.

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

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

A first step of etching using a mixed gas of a fluorine-based gas and an oxygen gas (O ₂ ) to a region (depth) where the support is not exposed, and a second step of etching with nitrogen gas (N ₂ ) and using a mixed gas of oxygen gas (O _2), preferably in the form including the over-etching is performed after the substrate is etched in the second step for performing etching up to the vicinity of areas (D) are exposed and the support is exposed desirable. Hereinafter, a specific method of dry etching, etching in the first step, etching in the second step, and overetching will be described.

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

(1) The etching rate (nm / min) in the first etching step and the etching rate (nm / min) in the second etching step are respectively calculated.

(2) The time for etching the desired thickness by the etching of the first step and the time for etching the desired thickness by the etching of the second step are respectively calculated.

(3) The etching of the first step is carried out in accordance with the etching time calculated in the above-mentioned (2).

(4) The etching of the second step is carried out in accordance with the etching time calculated in the above-mentioned (2). Alternatively, the etching time may be determined by end point detection, and the etching of the second step may be performed according to the determined etching time.

(5) Overetching time is calculated for the total time of (3) and (4) described above, and overetching is performed.

As the mixed gas used in the etching process in the first step, fluorine-based gas and oxygen gas (O ₂ ) are preferably included from the viewpoint of processing the organic material as the etching film into a rectangular shape. The etching process in the first step is performed by etching to a region where the support is not exposed, so that damage to the support can be avoided. The etching step and the overetching step in the second step are carried out in such a manner that after the etching is carried out up to the region where the support is not exposed by the mixed gas of the fluorine gas and the oxygen gas in the etching step of the first step, , A mixed gas of nitrogen gas and oxygen gas is preferably used for the etching treatment.

It is important to determine the ratio of the amount of etching in the first etching step to the amount of etching in the second etching step so as not to damage the rectangularity due to the etching treatment in the first etching step. The latter ratio in the total etching amount (the sum of the etching amount in the first etching step and the etching amount in the second etching step) is preferably in a range of more than 0% and not more than 50% And more preferably 10 to 20%. The etching amount refers to an amount calculated from the difference between the remaining film thickness of the etched film and the film thickness before etching.

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

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

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

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

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

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

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

When removing with a peeling liquid, the resist pattern formed on the colored pattern is only required to be removed, and even if a deposit as an etching product adheres to the side wall of the colored pattern, the deposit may not be completely removed. The sediment means that the etching product adheres to the side wall of the colored layer and is deposited.

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

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

Further, in order to efficiently clean the nozzles of the coating device discharging portion, the clogging of the pipe portion, the staining by the coloring composition or the pigment adhering, settling and drying into the applicator, it is preferable to use a solvent for the coloring composition of the present invention desirable. Also, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, Japanese Patent Application Laid-Open Nos. 2006-291191, 2007-2101, 2007-2102, 2007-281523, etc. can suitably be used.

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

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

Since the color filter of the present invention is used in the color filter of the present invention, it is excellent in light resistance, flame retardancy, and flatness.

The color filter of the present invention can be suitably used for a solid-state image pickup device such as a CCD and a CMOS, and is particularly suitable for a high-resolution CCD or CMOS exceeding one million pixels. The color filter for a solid-state imaging device of the present invention can be used, for example, as a color filter disposed between a light-receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing.

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

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

<Solid-state image sensor>

The solid-state image pickup device of the present invention includes the above-described color filter of the present invention or the color filter manufactured by the method of manufacturing the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the color filter according to the present invention and functions as a solid-state imaging device.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode made of polysilicon or the like are formed on a support, and only a photodiode light- A device shielding film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, and having a color filter for a solid-state imaging device of the present invention .

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

<Image Display Device>

The above-described color filter of the present invention or the color filter manufactured by the method of manufacturing a color filter of the present invention can be applied not only to solid-state image pickup devices but also to image display devices such as liquid crystal display devices and organic EL (Electro-Luminescence) 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 is capable of displaying a high-quality image with good display tones and excellent display characteristics.

For example, "electronic display device (Sasaki Akio, issued by Sakai High School 1990, published in 1990)", "display device (issued by Ibukisumi Akira, published in 1972) " The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, issued by Sakai High School Sakai 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology ".

The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kiyoshi Shootpan 1996) ". The present invention can also be applied to a liquid crystal display device such as a liquid crystal display device such as a transverse electric field driving method such as IPS (In-Plane Switching) or a pixel division method such as MVA (Multi-domain vertical alignment), a STN (Super-twisted nematic) (Twisted Nematic), VA (Vertically Aligned), OCS (Optically Compensated Splay), FFS (Fringe Field Switching), and R-OCB (Optically Compensated Bend).

The color filter in the present invention can also be provided in a bright, high definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. In the color filter of the present invention, since a color pigment having excellent color is good, color purity, light transmittance and the like are good and coloring pattern (pixel) is excellent in color tone, a COA type liquid crystal display device having high resolution and long- . Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described in, for example, page 43 of "EL, PDP (Plasma Display Panel), LCD display technology and the latest trend in the market "

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. As for these members, for example, "Market of Liquid Crystal Display Materials and Chemicals around 1994 (published by Shimadaro Corporation in 1994)", "2003 Present condition and future prospect of liquid crystal related market" Fuji Chimera Soken, published in 2003 ").

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

In addition, the present invention can be suitably used for display of micro-OLED (organic light-emitting diodes). For these image display methods, for example, "EL, PDP, &Quot; published by Toray Research Center Research Institute, 2001, "

When the color filter according to the present invention is used for a liquid crystal display device, high contrast can be realized when combined with a conventional three-wavelength tube of a cold cathode tube. In addition, a red LED, a green LED, ) -LED) as a backlight, it is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the object thereof. Unless otherwise stated, "%" and "part" are based on mass.

&Lt; Measurement method of weight average molecular weight >

The weight average molecular weight was measured by polystyrene conversion value measured by Gel Permeation Chromatography (GPC). Specifically, TSKgel Super AWM-H (a plasticizer, 6.0 mm ID × 15.0 cm) was used as a column and 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) was used as an eluent, using HLC-8220 Solution.

&Lt; Measurement method of acid value >

Acid value represents the weight of potassium hydroxide necessary to neutralize the acidic component per 1 g of solid content. Concretely, the measurement sample was dissolved in tetrahydrofuran / water = 9/1 mixed solvent and the obtained solution was stirred at 25 ° C using a potentiometric titration apparatus (trade name: AT-510, manufactured by Kyoto Denshi Kogyo) , And neutralized with a 0.1 M aqueous sodium hydroxide solution. Using the inflection point of the appropriate pH curve as an appropriate end point, the acid value was calculated by the following formula.

A = 56.11 x Vs x 0.1 x f / w

A: acid value (mgKOH / g)

Vs: Amount of 0.1 M sodium hydroxide aqueous solution required for titration (mL)

f: Potency of aqueous 0.1M sodium hydroxide solution

w: Weight of the sample to be measured (g) (in terms of solid content)

&Lt; Measurement of absorbance &

The absorbance at 25 캜 was measured with a UV-Vis-NIR spectrophotometer (trade name: Cary 5000, manufactured by Agilent Technologies, Inc.) using a cell having an optical path length of 1 cm.

<Synthesis Examples of Trialaryl Methane Dyes (A-tp-1), (A-tp-3), (A-tp-5) and (A-

(A-tp-1) and (A-tp-3) were prepared in the same manner as in the method described in paragraphs 0112 to 0114 of Japanese Patent Application Laid-Open No. 2000-162429 (Example 4 , (A-tp-5) and (A-tp-8) were synthesized.

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&Lt; Synthesis Example of Xanthene Compound (A-xt-104) >

&Lt; EMI ID =

&Lt; Synthesis of intermediate 1 &gt;

31 parts of DCSF (Spiro [3H-2,1-benzoxathiole-3,9 '- [9H] xanthene], 3', 6'- dichloro- 1,1- 67 parts of isopropylaniline, 17 parts of zinc chloride and 120 parts of sulfolane were placed in a flask and stirred at 200 ° C for 8 hours. Thereafter, the reaction mixture was cooled to room temperature, and the reaction solution was added dropwise to 600 parts of 2N hydrochloric acid, and the precipitated crystals were separated by filtration. The crystals were dispersed and washed with 600 parts of acetonitrile at 40 degrees, then filtered and air-dried for 10 hours to obtain 42.5 parts (yield: 82%) of intermediate 1.

&Lt; Synthesis of intermediate 2 &gt;

11 parts of the intermediate 1 and 50 parts of phosphorus oxychloride (POCl ₃ ) were placed in a flask and stirred at 60 ° C for 4 hours. Thereafter, the mixture was cooled to room temperature, the reaction solution was dropped into 150 parts of ice water, and the mixture was stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 20 parts of water, and then the obtained crystals were dissolved in 150 parts of chloroform and subjected to Celite filtration. The filtrate was separated into 100 parts of 5% brine and 100 parts of 15% brine. After drying with sodium sulfate, the mixture was concentrated under reduced pressure to obtain 12.1 parts (yield: 91%) of Intermediate 2.

&Lt; Synthesis of intermediate 3 &gt;

15 parts of pentafluorobenzenesulfonyl chloride and 300 parts of tetrahydrofuran (THF) were placed in a flask, and the internal temperature was cooled to -10 占 폚. Thereafter, 6.8 parts of 28% ammonia water (NH ₃ aq) was added dropwise so as to keep the reaction solution at 0 캜 or lower. After the dropwise addition, the mixture was stirred at 0 ° C for 1 hour, and then the reaction solution was filtered. The obtained filtrate was concentrated under reduced pressure to remove THF, and then 100 parts of water was added and stirred. The resulting solid was filtered, washed with water and blow-dried for 10 hours to obtain 11.7 parts (yield: 84%) of Intermediate 3.

&Lt; Synthesis of intermediate 4 &gt;

15 parts of the intermediate 3, 4.9 parts of 2-mercaptoethanol, and 100 parts of methanol were added to the flask, and the mixture was stirred at room temperature. 6.5 parts of triethylamine (TEA) was added dropwise thereto so that the temperature of the reaction solution did not exceed 30 占 폚. After stirring at room temperature for 1 hour and concentration under reduced pressure, ethyl acetate (90 parts), saturated brine (80 parts) and saturated aqueous sodium hydrogencarbonate (10 parts) were added. The aqueous layer was extracted with 90 parts of ethyl acetate, and then magnesium sulfate was added to the obtained organic layer. After filtration, the filtrate was concentrated under reduced pressure and air-dried for 10 hours to obtain 17 parts (yield: 92%) of Intermediate 4.

<< Synthesis of intermediate 5 >>

49 parts of the intermediate 4, 25 parts of 2-isocyanatoethyl acrylate (AOI, Showa Denko Co.), 0.2 part of dibutylhydroxytoluene (BHT), 95 parts of dimethylacetamide (DMAc) -600 (Nitto Chemical Co., Ltd.) was added to the flask, and the mixture was stirred at 85 占 폚 for 1 hour. Subsequently, 500 parts of ethyl acetate and 500 parts of saturated saline were added to carry out the liquid separation operation. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure. The resulting solid was suspended and washed with 170 parts of chloroform, filtered and air-dried to obtain 60 parts (yield: 84%) of Intermediate 5.

<< Synthesis of Xanthene Compound (A-xt-104) >>

5 parts of intermediate 5, 50 parts of methylene chloride and 3.4 parts of triethylamine (TEA) were added to the flask, and the mixture was stirred at room temperature. 10.8 parts of Intermediate 2 was added thereto, followed by stirring at room temperature for 2 hours. After completion of the reaction, 200 parts of chloroform, 500 parts of pure water and 200 parts of saturated saline solution were added to carry out the liquid separation operation. Sodium sulfate was added to the obtained organic layer, followed by dehydration, followed by filtration, and the filtrate was concentrated under reduced pressure. The resulting solid was dissolved in chloroform and purified by column chromatography using a chloroform / ethyl acetate solvent to obtain 12.5 parts (yield: 86%) of A-xt-104.

Synthesis Example of Xanthene Compounds (A-xt-101), (A-xt-110), (A-xt-117) and (A-

The xanthene compounds (A-xt-101), (A-xt-110), (A-xt-117) and .

[Chemical Formula 87]

&Lt; Synthesis Example of Thiol Compound >

As shown below, thiol compounds B-1 to B-12 were synthesized.

[Synthesis Example B-1]

Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP; , 12.0 parts of triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine were dissolved in 50.0 parts of N-methylpyrrolidinone (NMP) And heated. After cooling to room temperature, the reaction solution was added dropwise to a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate, followed by re-precipitation to obtain 12.5 parts of the thiol compound (B-1) shown below. It was confirmed that the proportion of the dye portion to the R ³ portion in the NMR measurement was 5.

[Formula 88]

[Synthesis Example B-2]

12.0 parts of the triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine in Synthesis Example B-1, 9.6 parts of the triarylmethane dye (A-tp-1) and 1.61 parts of triethylamine 1.34 10.5 parts of the thiol compound (B-2) was obtained in the same manner as in the above Synthesis Example B-1, except that the thiol compound It was confirmed by NMR measurement that the ratio of the dye moiety to the R ³ moiety was 4.

[Synthesis Example B-3]

12.0 parts of triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine in Synthesis Example B-1, 7.2 parts of triarylmethane dye (A-tp-1) and 1.01 part of triethylamine 8.3 parts of the thiol compound (B-3) was obtained in the same manner as in the above Synthesis Example B-1, except that the thiol compound (B-3) It was confirmed by NMR measurement that the ratio of the dye moiety to the R ³ moiety was 3.

[Synthesis Example B-4]

12.0 parts of triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine in Synthesis Example B-1, 4.8 parts of triarylmethane dye (A-tp-1) and 0.48 part of triethylamine 6.0 parts of thiol compound (B-4) was obtained in the same manner as in Synthesis Example B-1, except that the compound It was confirmed by NMR measurement that the ratio of the dye moiety to the R ³ moiety was 2.

[Synthesis Example B-5]

Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP; 2.0 parts of triethylammonium dye (A-tp-3) and 0.21 part of triethylamine were dissolved in 50.0 parts of N-methylpyrrolidinone (NMP) And heated. After cooling to room temperature, the reaction solution was added dropwise to a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and the mixture was re-dissolved to obtain 12.3 parts of the thiol compound (B-5).

(89)

[Synthesis Example B-6]

Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP; (Manufactured by SC Yuki Kagaku Kogyo Co., Ltd.) and 9.4 parts of a triarylmethane dye (A-tp-8) were dissolved in 50.0 parts of N-methylpyrrolidinone (NMP) and heated to 80 ° C under a nitrogen atmosphere. 2,2'-azobis (isobutyrate) dimethyl [V-601; Manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 80 占 폚 for 2 hours. After adding 0.13 parts of V-601, the mixture was heated and stirred at 80 DEG C for 2 hours, and then cooled to room temperature. The reaction solution was added dropwise to a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and re-dissolved to obtain 10.2 parts of the thiol compound (B-6).

(90)

[Synthesis Example B-7]

Dipentaerythritol hexakis (3-mercaptopropionate) in Synthesis Example B-1 (DPMP; (Trade name, product of SC Yuki Kagaku Kogyo Co., Ltd.), 12.0 parts of triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine, pentaerythritol tetra (3-mercaptopropionate) (B-7) was obtained in the same manner as in the above Synthesis Example B-1, except that 2.0 parts of the above-mentioned compound (A-xt-101) and 9.9 parts of triethylamine 10.7 parts were obtained.

[Formula 91]

[Synthesis Example B-8]

11.6 parts of the triarylmethane dye (A-tp-3) and 0.21 part of triethylamine in Synthesis Example B-5 were changed to 14.2 parts of the xanthene compound (A-xt-104) and 0.26 part of triethylamine , 14.4 parts of the thiol compound (B-8) was obtained in the same manner as in the above Synthesis Example B-5.

&Lt; EMI ID =

[Synthesis Example B-9]

11.6 parts of the triarylmethane dye (A-tp-3) and 0.21 part of triethylamine in Synthesis Example B-5 were changed to 11.4 parts of the xanthene compound (A-xt-104) and 0.21 part of triethylamine , 12.1 parts of the thiol compound (B-9) was obtained in the same manner as in the above Synthesis Example B-5.

[Synthesis Example B-10]

11.6 parts of the triarylmethane dye (A-tp-3) and 0.21 part of triethylamine in Synthesis Example B-5 were changed to 8.6 parts of the xanthene compound (A-xt-104) and 0.16 part of triethylamine , 9.5 parts of the thiol compound (B-10) was obtained in the same manner as in Synthesis Example B-5.

[Synthesis Example B-11]

Except that 9.4 parts of the triarylmethane dye (A-tp-8) and 4.2 parts of the squarylium compound (Ak-1) in Synthesis Example B-6 were used in place of Synthesis Example B- To obtain 5.6 parts of a thiol compound (B-11).

&Lt; EMI ID =

[Synthesis Example B-12]

The procedure of Synthesis Example B-6 was repeated except that 9.4 parts of the triarylmethane dye (A-tp-8) in Synthesis Example B-6 was changed to 4.2 parts of the cyanide (A-pm-1) , And 5.6 parts of thiol compound (B-12).

(94)

<Synthesis of Dispersant Having Pigment Structure>

[Synthesis Example C-1]

5.0 parts of the thiol compound (B-1) obtained in Synthesis Example B-1, 0.96 part of methacrylic acid (MAA), and 9.0 parts of cyclohexanone was heated to 80 占 폚 in a nitrogen stream. To this was added 2,2'-azobis (isobutyrate) dimethyl [V-601; Wako Junyaku Co., Ltd.] was added, and the mixture was heated and stirred at 80 占 폚 for 2 hours. After 0.077 parts of V-601 was added, the mixture was heated and stirred at 80 占 폚 for 2 hours and further stirred at 90 占 폚 for 2 hours. After cooling to room temperature, 30.7 parts of cyclohexanone, 0.14 parts of tetrabutylammonium bromide (TBAB) and 0.79 parts of glycidyl methacrylate (GMA) were added and the mixture was heated and stirred at 80 占 폚 for 18 hours. After cooling to room temperature, the reaction solution was added dropwise to a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and re-dissolved to obtain a dispersant (C-1) having the following dye structure. The weight average molecular weight (polystyrene reduced value) of the dispersant (C-1) having a pigment structure was 11600, and the acid value was found to be 46 mgKOH / g by titration using a 0.1 N aqueous sodium hydroxide solution. By NMR, the molar ratio of the dye structure / MAA / MAA to the adduct of GMA was 5/6/6, and the number of repetitions of the P moiety was calculated as 12 on average. Further, a solution containing 0.01 mg / ml of a dispersant (C-1) having a pigment structure dissolved in tetrahydrofuran (THF) (concentration adjusted to a maximum absorbance of 1.0) Was measured using a cell having an optical path length of 1 cm, the maximum absorption wavelength (? Max) was 615 nm, and the specific absorption of the maximum absorption wavelength (? Max) was 60.

&Lt; EMI ID =

[Synthesis Examples C-2 to C-12]

Except that the amounts of the thiol compound, the polymerizable monomer, the amount of V-601, the amount of glycidyl methacrylate, and the amount of tetrabutylammonium bromide were changed to the following Table 1, , And dispersing agents (C-2) to (C-12) having a pigment structure were obtained.

&Lt; Measurement of specific absorbance &

Each dye was dissolved in tetrahydrofuran (THF), adjusted to a concentration at which the maximum absorbance at a wavelength of 400 nm to 800 nm was 1.0, and the absorbance of this solution at 25 캜 was measured using a cell having an optical path length of 1 cm Based on the formula (A?).

E = A / (cxl) ... (A?)

In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,

A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,

l represents the cell length in cm,

c represents the concentration of the pigment in the solution, in which the unit is expressed in mg / ml.

[Table 1]

[Synthesis Example C-13]

5.0 parts of the thiol compound (B-1) obtained in Synthesis Example B-1, 0.96 part of methacrylic acid (MAA), 10.0 parts of methyl methacrylate and 19.5 parts of N-ethylpyrrolidone was introduced into a 90 Lt; 0 &gt; C. To this was added 2,2'-azobis (isobutyrate) dimethyl [V-601; Wako Junyaku Co., Ltd.), and the mixture was heated and stirred at 90 占 폚 for 1.5 hours. After 0.77 parts of V-601 was added, the mixture was heated and stirred at 90 占 폚 for 1.5 hours, and further heated and stirred at 90 占 폚 for 2 hours. After cooling to room temperature, the reaction solution was added dropwise to a mixed solvent of 500 mL of hexane and 500 mL of ethyl acetate and re-coated to obtain a dispersant (C-13) having the following dye structure. The weight average molecular weight (polystyrene reduced value) of the dispersant (C-13) having a pigment structure was 27,500, and the acid value was 39 mgKOH / g by titration using a 0.1 N aqueous sodium hydroxide solution. By NMR, the molar ratio of the dye structure / MAA / MMA was 5/12/108. Further, a solution containing 0.01 mg / ml of the dye (C-45) dissolved in tetrahydrofuran (THF) was prepared. The absorbance of this solution at 25 캜 was measured using a cell having an optical path length of 1 cm, The maximum absorption wavelength (? Max) was 615 nm and the specific absorption maximum of the maximum absorption wavelength (? Max) was 25.

&Lt; EMI ID =

[Synthesis Examples C-14 to 24]

Dispersants C-14 to C-24 having a pigment structure were obtained in the same manner as in Synthesis Example C-13, except that the amount of the thiol compound, the amount of the polymerizable monomer, and the amount of the photopolymerization initiator were changed to those shown in Table 2 below. .

[Table 2]

The types of the polymerizable monomers listed in Tables 1 and 2 are shown below.

[Formula 97]

Dispersant D-1 having a dye structure of the structure shown below was synthesized using a triarylmethane dye (A-tp-1) as a dye. The detailed operation will be described below.

&Lt; Synthesis of macromonomer (N-1) >

35.0 g (0.27 mol) of 2-ethylhexanol, 307.1 g (2.70 mol) of? -Caprolactone and 0.20 g of monobutyltin oxide were heated at 90 占 폚 for 5 hours and then at 110 占 폚 for 10 hours in a nitrogen atmosphere to obtain poly Ester monohydroxy compound was obtained. The termination of the reaction was confirmed by measuring the disappearance of epsilon -caprolactone by NMR. After cooling to 80 ° C, 0.071 g of 2,6-ditertiarybutyl-4-methylphenol and 42.3 g (0.27 mol) of 2-methacryloyloxyethyl isocyanate were added and the mixture was stirred at 80 ° C. for 3 The reaction was carried out for a time to obtain a macromonomer N-1. The termination of the reaction was confirmed by measuring the disappearance of 2-methacryloyloxyethyl isocyanate by NMR. The weight average molecular weight of the macromonomer N-1 as determined by GPC was 2200.

[Synthesis Example D-1]

(98)

A triarylmethane dye (A-tp-101) was synthesized according to the method described in Japanese Patent Laid-Open No. 2000-162429.

15 g of triarylmethane dye (A-tp-101), 12 g of macromonomer N-1 and 3.5 g of methacrylic acid were dissolved in 0.75 g of dodecane thiol, did. 2,2'-azobis (isobutyrate) dimethyl [V-601; Wako Junyaku Co., Ltd.), and the mixture was heated and stirred at 80 占 폚 for 2 hours. After addition of 1.70 parts of V-601, the mixture was heated and stirred at 80 占 폚 for 2 hours and further stirred at 90 占 폚 for 2 hours. After cooling to room temperature, the reaction solution was added dropwise to a mixed solvent of 500 mL of hexane and 500 mL of ethyl acetate, and the mixture was re-dissolved to obtain a dispersant (D-1) having a pigment structure. The dispersant (D-1) having a pigment structure had a weight average molecular weight (in terms of polystyrene) of 7400 and an acid value of 110 mgKOH / g by titration using a 0.1 N aqueous sodium hydroxide solution. By NMR, the molar ratio of the dye structure / N-1 / MMA was 10/74/16. Further, a solution containing 0.01 mg / ml of the dye (D-1) dissolved in tetrahydrofuran (THF) was prepared. The absorbance of this solution at 25 캜 was measured using a cell having an optical path length of 1 cm, The maximum absorption wavelength (? Max) was 615 nm and the specific absorption maximum of the maximum absorption wavelength (? Max) was 20.

[Synthesis Examples D-2 to 16]

Except that the amounts of the dye monomer, the other polymerizable monomer, the amount of V-601, and the amount of the dodecaine thiol were changed to the contents shown in the following Table 3, the dispersant D- 2 to D-16 were obtained. Further, N-2 is AA-6 (Macro monomer of Toagosei Co., Ltd.). A-pm-2 and A-k-2 represent compounds of the following structures.

[Formula 99]

Comparative dye 1: Triarylmethane dye (A-tp-1): The following structure

Comparative dye 2: xanthene compound (A-xt-105): The following structure

(100)

(Synthesis of comparative dispersing agents 4 to 6)

Comparative Dyes 4 to 6 having the following structural formulas were synthesized by the method described in Japanese Patent Application Laid-Open No. 2007-277514, paragraphs 0272 to 0326. Comparative Dispersant 4: The following structure (Synthesis Example C-9 of Japanese Patent Application Laid-Open No. 2007-277514)

M = 1, n = 5 Comparative Dispersing Agent 5 The following structure (Synthesis Example C-25 of JP-A No. 2007-277514)

M = 1, n = 3 Comparative Dispersing Agent 6 The following structure (Synthesis Example C-4 of Japanese Patent Application Laid-Open No. 2007-277514)

In the formula, m = 1, n = 5 Comparative dispersant 4

(101)

Comparative Dispersant 5

&Lt; EMI ID =

Comparative Dispersant 6

&Lt; EMI ID =

(Synthesis of Comparative Dispersant 7)

A comparative dye 7 having the following structural formula was synthesized by the method described in Japanese Patent Application Laid-Open No. 2011-118060, Paragraph No. 0136. That is, 8 g of methacrylic acid, 8.3 g of macromonomer (DOA Gosei, AA-6), 2.6 g of monomer a (the following structure) having a dipyrammethene dye skeleton, 30 g of propylene glycol methyl ether acetate, 0.2 g of dodecane thiol was stirred under nitrogen and maintained at 75 占 폚. Then, 0.06 part of a photopolymerization initiator (V-601, Wako Pure Chemical Industries, Ltd.) was added and stirred for 2 hours. Followed by stirring at 90 占 폚 for 2 hours. And cooled to room temperature to obtain a dispersant having a pigment structure (comparative dye 7). The weight average molecular weight (in terms of polystyrene) of the comparative dye 7 was 12,000, and the acid value was 100 mgKOH / g by titration using a 0.1 N aqueous sodium hydroxide solution. Further, a solution containing 0.01 mg / ml of the dye (D-1) dissolved in tetrahydrofuran (THF) was prepared. The absorbance of this solution at 25 캜 was measured using a cell having an optical path length of 1 cm, The maximum absorption wavelength (max) was 550 nm, and the maximum absorption wavelength (max) was 18.

A monomer having a dipyrammethene dye skeleton a

&Lt; EMI ID =

[Table 3]

&Lt; Example 1 >

1. Preparation of resist solution

The following composition was mixed and dissolved to prepare a resist solution for the undercoat layer.

Composition of resist solution for undercoat layer

Solvent: propylene glycol monomethyl ether acetate 19.20 parts

Solvent: Ethyl lactate 36.67 parts

40% PGMEA solution of alkali soluble resin: benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) 30.51 part

占 ethylenically unsaturated double bond-containing compound: dipentaerythritol hexaacrylate, KAYARAD DPHA (Nippon Kayaku) 12.20 parts

Polymerization inhibitor: 0.0061 part of p-methoxyphenol

Fluorine-based surfactant: F-475, DIC 0.83 part

Photopolymerization initiator: 0.586 part of a trihalomethyltriazine based photopolymerization initiator (TAZ-107, Midori Kagaku)

2. Fabrication of silicon wafer substrate with undercoat layer

The 6-inch silicon wafer was heated in an oven at 200 캜 for 30 minutes. Subsequently, a resist solution for the undercoat layer was applied on the silicon wafer so that the dry film thickness became 1.5 占 퐉 and further heated and dried in an oven at 220 占 폚 for 1 hour to form an undercoat layer, .

3. Preparation of coloring composition

3-1. Preparation of blue pigment dispersion

&Lt; Preparation of Pigment Dispersion P-1 (C.I. Pigment Blue 15: 6 Dispersion)

Pigment dispersion P-1 (C dispersion of Pigment Blue 15: 6) was prepared in the following manner.

19.4 parts by mass (average primary particle diameter: 55 nm) of CI Pigment Blue 15: 6 (hereinafter, also referred to as "PB 15: 6") and 20.95 parts by mass of dispersant C- And 275 parts by mass were mixed and dispersed for 3 hours by means of a bead mill (zirconia beads having a diameter of 0.3 mm). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ by using a high-pressure disperser NANO-3000-10 (Nippon Bionish) equipped with a further pressure reducing mechanism. This dispersion treatment was repeated ten times to obtain a CI Pigment Blue 15: 6 dispersion as a pigment dispersion. The average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (Nikkiso Co., Ltd.)) with respect to the obtained CI Pigment Blue 15: 6 dispersion.

<Preparation of Pigment Dispersion P-2 to P-42, Comparative Dispersions P-1 to P-7>

Pigment dispersions P-2 to P-42, comparative dispersions P-1 to P-1 were prepared in the same manner as in the preparation of pigment dispersion P-1, P-7 was prepared.

PR means C. I. Pigment Red, and PG means C. I. Pigment Green.

Further, Comparative Dispersion P-3 does not contain a dispersant having a pigment structure and a comparative colorant.

[Table 4]

&Lt; Preparation of Pigment Dispersion P-43 >

Pigment dispersion P-43 (a dispersion of CI Pigment Blue 15: 6) was prepared as follows.

Namely, 24.56 parts by mass (average primary particle diameter: 55 nm) of CI Pigment Blue 15: 6 (hereinafter also referred to as "PB 15: 6") and 12.28 parts by mass of dispersant C- 3.51 parts of a pigment dispersant BY-161 having no structure (manufactured by BYK) and 275 parts of PGMEA was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm in diameter) for 3 hours. Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ by using a high-pressure disperser NANO-3000-10 (Nippon Bionish) equipped with a further pressure reducing mechanism. This dispersion treatment was repeated ten times to obtain a CI Pigment Blue 15: 6 dispersion as a pigment dispersion. The average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (Nikkiso Co., Ltd.)) relative to the obtained CI Pigment Blue 15: 6 dispersion.

&Lt; Preparation of Pigment Dispersion P-44 >

Pigment dispersion P-44 was prepared in the same manner as in the preparation of pigment dispersion P-43 except that the dispersant having a pigment structure was changed to D-8 and the pigment dispersant having no pigment structure was changed to E1 (the following structure) did.

&Lt; EMI ID =

Mw = 20000, x / y = 50/50 (mass ratio), n = 20, acid value = 100 mgKOH / g

3-2. Preparation of coloring composition

The following components were mixed, dispersed and dissolved, and filtered through a 0.45 占 퐉 nylon filter to obtain a colored composition. The proportion (unit) of the pigment in the solid content is 33% and the proportion of the dispersing agent is 36%.

Organic solvent (cyclohexanone): 17.12 parts

Alkali-soluble resin 1 (the following J1): 1.23 parts (solid content 0.37 part, solid content concentration 30%)

Alkali-soluble resin 2 (ARC Liqueur RD-F8 (Nippon Shokubai)): 0.23 parts

Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.975 parts

Pigment Dispersion P-1 (dispersion by C I. Pigment Blue 15: 6 and dispersant C-1, PGMEA solution, solid concentration 12.8%): 61.50 parts

Polymerizable compound Z-1 (ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (Shin Nakamura Kagaku)): 1.96 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

Fluorine-based surfactant (DIC F475, 1% PGMEA solution): 2.50 parts

Alkali-soluble resin J1

&Lt; EMI ID =

4. Fabrication of color filter (coloring pattern)

4-1: Fabrication of color filter using coloring composition by photolithography

The coloring composition prepared above was applied on the undercoat layer of the silicon wafer with the undercoat layer prepared above to form a colored layer (coating film). Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 1 탆.

Subsequently, the pattern was passed through an island pattern mask having a square of 1.0 m at a wavelength of 365 nm and exposed at an exposure dose of 50 to 1200 mJ / cm ² using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon).

Thereafter, the silicon wafer substrate on which the coated film was irradiated was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, made by Chemtronics), and using CD-2000 (Fuji Film Electronic Materials Co., Ltd.) Followed by puddle development at 23 DEG C for 60 seconds to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.

The silicon wafer on which the coloring pattern was formed was fixed to a horizontal rotary table by a vacuum chucking method and purified water was supplied from a spray nozzle through a nozzle in a shower shape while rotating the silicon wafer at a rotation speed of 50 rpm by a rotary device, Followed by spray drying, and post baking was performed with a hot plate at 200 占 폚 for 300 seconds to obtain a coloring pattern (color filter) having a film thickness of 1 占 퐉 on a silicon wafer.

Thus, a silicon wafer on which a colored pattern having a coloring pattern (color filter) was formed on an undercoat layer of a silicon wafer with an undercoat layer was obtained.

Thereafter, the size of the colored pattern was measured using a measurement SEM "S-9260A" (manufactured by Hitachi High-Technologies Corporation).

The development residue was evaluated using an exposure amount of the coloring pattern having a pattern size of 1.0 mu m.

&Lt; Evaluation of development residue &

The outside of the formation area (unexposed area) of the colored pattern in the silicon wafer was observed at a magnification of 30,000 times using a scanning electron microscope and evaluated according to the following evaluation criteria.

A Good: No residue was observed at any portion outside the coloring pattern forming region (unexposed portion).

B Slightly fine: Residues were slightly confirmed outside the coloring pattern forming area (unexposed area), but there was no problem in practical use.

C Sufficient: Residues were observed outside the coloring pattern forming area (unexposed area). The development condition was changed from a puddle development at 23 DEG C for 60 seconds to a puddle development at 23 DEG C for 180 seconds, and there was no practical problem.

D insufficient: Residues were confirmed to be prominent outside the coloring pattern forming region (unexposed portion). Also, even if the developing conditions were changed from 23 ° C for 60 seconds to 23 ° C for 180 seconds and then to a puddle development at 23 ° C from the puddle development, the residue was confirmed to be a problem in practical use.

<My discoloration>

The coloring composition was coated on a glass substrate using a spin coater so as to have a film thickness of 0.6 mu m and subjected to a heat treatment (prebaking) for 120 seconds using a hot plate at 100 deg. Subsequently, a heat treatment (post-baking) was performed using a hot plate at 220 캜 for 300 seconds to produce a cured film.

The color filter thus obtained was measured for its transmittance in a wavelength range of 300 nm to 800 nm with a spectrophotometer (reference: glass substrate) of ultraviolet visible infrared spectrophotometer UV3600 (Shimadzu Corporation). Further, differential interference images were observed on a reflection observation (magnification: 50 times) using an OLYMPUS optical microscope BX60.

Subsequently, the film was immersed in an alkali developing solution FHD-5 (FUJIFILM ELECTRONIC MATERIALS) for 5 minutes, dried and then again subjected to spectroscopic measurement to determine the transmittance variation before and after the solvent immersion (the transmittance before solvent immersion was T0, T1 &lt; / RTI &gt; &lt; RTI ID = 0.0 &gt; T1), &lt; / RTI &gt;

<< Evaluation Criteria >>

A: Good When the transmittance variation before and after solvent immersion in the entire region of 300 nm to 800 nm is less than 2%

B: slightly good The transmittance variation before and after solvent immersion in the entire region of 300 nm to 800 nm is 2% or more and less than 5%

C: sufficient transmittance variation before and after solvent immersion in the entire region of 300 nm to 800 nm is 5% or more and less than 10%

D: insufficient change in transmittance before and after solvent immersion in the entire region of 300 nm to 800 nm is 10% or more

<Light resistance>

The coloring composition prepared above was applied to a glass substrate using a spin coater (manufactured by Mikasa) to form a coating film. Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of this coating film was 0.6 탆. Subsequently, heating was performed at 200 DEG C for 5 minutes to cure the coating film to form a colored layer.

A quartz inner filter, a 275 nm cut outer filter, an illuminance of 75 mw / m ² (300 to 400 nm), a black panel temperature of 63 캜, and a cut outer filter using a light resistance tester (Suga Shikenki SX- ) And a humidity of 50% for 10 hours.

The color difference (? E * ab) before and after heating was measured by a spectrophotometer MCPD-3000 (manufactured by Otsuka Denka Co., Ltd.). Based on the measured color difference (? E * ab), the light resistance was evaluated according to the following evaluation criteria. The smaller this value is, the better the light resistance is. The evaluation results are shown in the following table. A and B are levels at which there is no problem in actual use.

<< Evaluation Criteria >>

A Good: ΔE * ab is 3 or less

B slightly better:? E * ab is greater than 3 and less than 5

C Sufficient: ΔE * ab greater than 5 and less than 10

D insufficient: ΔE * ab is greater than 10

&Lt; Roughness (color unevenness) >

The obtained monochromatic color filter (coloring pattern) was provided between the observation lens of the optical microscope and the light source, the light was irradiated toward the observation lens, and the state of the transmitted light was observed by an optical microscope equipped with a digital camera with a magnification of 1000 times . The digital camera installed in the optical microscope is equipped with a CCD of 128 megapixels, and the film surface in the transmitted light state is photographed. The photographed image was saved as data (digital image) digitally converted into an 8-bit bitmap format.

In addition, the photographing of the surface of the coating film of the colored pattern was carried out for arbitrarily selected 20 regions. The digitally converted data was obtained by digitizing the photographed image as the density distribution of 256 gradations (gradation) ranging from 0 to 255 in the luminance of the B color.

Subsequently, for the stored digital images, one grid size was divided into grid shapes so as to correspond to a square of 2 mu m on the actual plate, and the luminance in one segment was averaged. In this embodiment, since an optical image of 1000 times magnification is photographed with a digital camera of 128 million pixels, 2 mu m on the actual plate becomes 2 mm on the photographed image, and the image size on the display is 452 mm x 352 mm, The total number of compartments in one area was 39776.

The average luminance of one arbitrary section and all adjacent sections adjacent thereto was measured with respect to the whole section of each area. The average number of significant subdivisions of the total area and the average total number of the significant subdivisions of the total area are 39957 total areas (39776) in each area, (Hereinafter, simply referred to as "ratio"). The smaller the value, the less the color unevenness (roughness) is judged. It is judged that the number of significant subdivisions is 800 or less and the ratio is 3% or less and there is no problem in practical use.

<< Evaluation Criteria >>

A: The number of significant subdivisions is less than 500, the ratio is less than 2%

B: The number of significant subdivisions is 800 or less and the ratio is 3% or less (except for the case of A)

C: a level that is at least one of a significant number of divisions greater than 800 and a ratio exceeding 3%, which is a practical problem, and which does not correspond to A and B above.

&Lt; Examples 2 to 49 and Comparative Examples 1 to 7 >

The pigment dispersion P-1, the photopolymerization initiator I-2, the alkali-soluble resin J1 and the polymerizable compound Z-1 were changed as shown in the following table in "3-2 Preparation of a colored composition" in Example 1 A coloring composition was prepared in the same manner as in Example 1 except that the development residue, the discoloration resistance, the light resistance and the roughness were evaluated in the same manner as in Example 1.

Photopolymerization initiator:

&Lt; EMI ID =

Alkali-soluble resins J2 to J4:

(108)

J1 acid value: 195 mg KOH / g, J2 acid value: 51 mg KOH / g, J3 acid value: 49 mg KOH / g, J4 acid value:

Polymerizable compound

Z-1: Ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester

A-DPH-12E (Shin Nakamura Kagaku Co.)

Z-2: dipentaerythritol hexaacrylate, KAYARAD DPHA (Nippon Kayaku)

Z-3: Ethoxylated (4) pentaerythritol tetraacrylate, SR494 (Sartomer)

Z-4: Ethoxylated (3) trimethylolpropane acrylate, SR454 (Sartomer)

Z-5: Ethoxylated (6) trimethylolpropane acrylate, SR499 (Sartomer)

Z-6: KAYARAD DPCA-60 (Nippon Kayaku)

Z-7: Tris (2-hydroxyethyl) isocyanurate triacrylate, SR368 (Sartomer)

[Table 5]

[Table 6]

From the above table, it was found that the discoloration can be suppressed and the light resistance can be improved when the pigment dispersion of Examples is used. Further, it was found that the development residue and the roughness can be further reduced.

On the other hand, it was found that, in the case of using the pigment dispersion of the comparative example, it is difficult to achieve both suppression of discoloration and improvement in light resistance.

4-2: Fabrication and evaluation of color filters by dry etching process

(Preparation of colored composition for dry etching)

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

Organic solvent (cyclohexanone): 17.12 parts

Epoxy resin JER1031S (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 180-220 (g / eq.)): 4.395 parts

Pigment dispersion P1 (C.I. Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 75.97 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

Fluorine-based surfactant (DIC agent, F475, 1% PGMEA solution): 2.50 parts

(Fabrication of color filter using color curable composition by dry etching)

The colored composition for dry etching obtained above was applied onto a glass substrate of 7.5 cm x 7.5 cm using a spin coater and heated at 200 캜 for 5 minutes using a hot plate to cure the coated film, Layer. The film thickness of this colored layer was 0.5 mu m.

Subsequently, a positive type photoresist "FHi622BC" (manufactured by Fuji Film Electronics Materials Co., Ltd.) was applied and prebaked at 90 DEG C for 1 minute to form a photoresist layer having a thickness of 0.8 mu m.

Then, the photoresist layer was subjected to pattern exposure at an exposure dose of 350 mJ / cm ² using an i-line stepper (manufactured by Canon Inc.), and the resist layer was heated for 1 minute at a temperature at which the temperature of the photoresist layer or the ambient temperature reached 90 占 폚 Treatment. Thereafter, development processing was performed for one minute with a developing solution "FHD-5" (manufactured by FUJIFILM ELECTRONIC MATERIALS), and further post-baked at 110 DEG C for one minute to form a resist pattern. The size of the resist pattern was formed to be 1.0 μm on one side in consideration of the etching conversion difference (reduction in pattern width due to etching).

Next, the obtained glass substrate was attached to an 8-inch silicon wafer and RF (Radio Frequency) power: 800 W, antenna bias: 400 W, wafer bias: 200 W, The internal pressure of the chamber was 4.0 Pa, the substrate temperature was 50 DEG C, and the gas species and flow rate of the mixed gas were 80 mL / min. For CF ₄ , 40 mL / min for O ₂ and 800 mL / Was subjected to an etching treatment.

Then, in the same etching chamber, the gas species and the flow rate of the mixed gas were set to 500 mL / min (N _{2) in an} RF power of 600 W, an antenna bias of 100 W, a wafer bias of 250 W, an inner pressure of the chamber of 2.0 Pa, (N ₂ / O ₂ / Ar = 10/1/10), O _{2 was} 50 mL / min, and Ar was 500 mL / min, and the second stage etching treatment and overetching treatment were performed for 28 seconds.

After performing the dry etching under the above conditions, the resist was peeled off at 50 DEG C for 120 seconds using a photoresist peeling solution "MS230C" (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD.) To form a blue coloring pattern . Further, washing with pure water and spin drying were performed, and dehydration baking treatment was then performed at 100 ° C for 2 minutes. Thus, a color filter was obtained.

&Lt; Evaluation of development residue &

The outside of the formation area (unexposed area) of the colored pattern in the silicon wafer was observed with a scanning electron microscope at a magnification of 30,000 times and evaluated according to the following evaluation criteria. As a result, residues were not observed at all outside the coloring pattern forming area (unexposed area).

&Lt; Evaluation of discoloration >

Evaluation of discoloration in the interior was carried out in the same manner as in the production of the color filter using the color composition by the photolithography method. As a result, the transmittance variation before and after immersion in the solvent was less than 2% in the entire region of 300 nm to 800 nm.

&Lt; Evaluation of light resistance &

The light resistance was evaluated in the same manner as in the production of the color filter using the color composition by the photolithography method. As a result,? E * ab was 3 or less and was good.

&Lt; Evaluation of roughness (color unevenness) >

(Color heterogeneity) was evaluated in the same manner as in the production of the color filter using the color composition by the photolithography method. As a result, the number of significant subdivisions was less than 500, and the ratio was less than 2%, which was an excellent level.

Claims (24)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete A method for producing a pigment dispersion containing a dispersant having a pigment structure, a pigment, and a solvent,
And dispersing the pigment in the presence of a dispersant and a solvent having a pigment structure,
Wherein the dispersant having the dye structure has a dye structure selected from a triarylmethane dye, a xanthine dye, a cyanine dye and a squarylium dye,
The dispersing agent having the dye structure is a pigment multimer having two or more of the dye structures in the same molecule and has a specific absorption of 5 or more at a maximum absorption wavelength in the range of 400 nm to 800 nm represented by the following formula (A?),
Wherein the content of the solvent is 50 to 95% by mass with respect to the total mass of the pigment dispersion liquid;
E = A / (cxl) ... (A?)
In the formula (A?), E represents a non-absorbance at a maximum absorption wavelength in the range of 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength in the range of 400 nm to 800 nm,
l represents the cell length in cm,
c represents the concentration of the dispersant having a pigment structure in the solution, in which the unit is expressed in mg / ml. delete delete 18. The method of claim 16,
Wherein the dye structure of the dispersing agent having the dye structure comprises an anion site and the anion site is selected from the group consisting of a sulfonic acid anion, a carboxylic acid anion, a tetraarylborate anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- A group containing a structure represented by the following formula (A2), and a group including a structure represented by the following formula (A2);
In formula (A1)
[Chemical Formula 1]

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-;
In general formula (A2)
(2)

In the general formula (A2), R ³ represents -SO ₂ - or -CO-; R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN. The method according to claim 16 or 19,
Wherein the pigment is contained in an amount of 80 to 150 parts by mass based on 100 parts by mass of the dispersant having the pigment structure. The method according to claim 16 or 19,
Wherein the weight average molecular weight of the dispersant having the dye structure is not less than 3000 and not more than 50000. The method according to claim 16 or 19,
Wherein the dispersant having the dye structure has an acid value of 27 mgKOH / g or more and less than 200 mgKOH / g. A process for producing a colored composition, comprising the steps of: preparing a pigment dispersion by the process for producing a pigment dispersion according to claim 16 or 19; and mixing the obtained pigment dispersion with the curable compound. 24. The method of claim 23,
And the photopolymerization initiator is further mixed.