KR20190035929A - Coloring composition, color filter, method for forming pattern, method for producing color filter, solid-state imaging element, image display device, and method for producing dye multimer - Google Patents

Abstract

The coloring composition includes a pigment oligomer represented by the general formula (1) and a polymerizable compound. In the general formula (1), P represents a linking group of n, Q represents a polymer chain containing a repeating unit having a dye structure, and an average value of the number of repeating units having n pigment Q- And n represents an integer of 3 to 10.
P- (Q) _n ... (One)

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring composition, a color filter, a pattern forming method, a manufacturing method of a color filter, a solid-state image pickup device, an image display device and a manufacturing method of a colorant multimeter (COLORING COMPOSITION, COLOR FILTER, METHOD FOR PRODUCING COLOR FILTER, SOLID- STATE IMAGING ELEMENT, IMAGE DISPLAY DEVICE, AND METHOD FOR PRODUCING DYE MULTIMER}

The present invention relates to a coloring composition. And more particularly to a coloring composition suitable for a color filter used in a solid-state image pickup device, an image display device, and the like. Further, the present invention relates to a color filter, a solid-state image pickup device and an image display device using a coloring composition. The present invention also relates to a method of forming a pattern using a coloring composition, a method of producing a color filter, and a method of producing a colorant.

2. Description of the Related Art In recent years, demand for solid-state image pickup devices such as charge coupled device (CCD) 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 there is a growing demand for further high sensitivity and miniaturization. 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.

Colorants used in color filters are required to have the following properties in common. That is, it is required to have preferable light absorption characteristics on the color reproducibility, good light resistance, and the like.

On the other hand, Patent Document 1 discloses a pigment dispersant having 2 to 9 moieties in one molecule, having a site capable of adsorbing the pigment. A moiety having 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 an oxygen atom, a hydrocarbon group having 4 or more carbon atoms, A silyl group, an epoxy group, an isocyanate group, a hydroxyl group, and an ionic functional group.

Patent Document 1: JP-A-2008-222950

In a coloring composition used for a color filter or the like, further improvement in light resistance, flame retardancy and flatness is required.

Patent Document 1 is an invention relating to a pigment dispersant. Patent Document 1 discloses that an organic pigment structure may be used as a site having adsorption ability to a pigment. Since it is preferable that the pigment dispersant does not have a color, a site having an adsorption ability to a pigment has a light absorbance You need to choose a small structure. Also, in Patent Document 1, there is no motivated statement that a pigment dispersant is used as a colorant.

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object thereof is to provide a coloring composition excellent in light resistance, flame retardancy and flatness. It is also an object of the present invention to provide a color filter, a pattern forming method, a method of manufacturing a color filter, a solid-state image pickup device, an image display device, and a method of producing a colorant multimer.

As a result of a detailed investigation, the inventors of the present invention have found that a colored composition excellent in light resistance, flame retardancy and flatness can be obtained by using a dye multimer having n polymer chains in which n polymer chains including a repeating unit having a dye structure are bonded, The present invention has been accomplished on the basis of these findings. Therefore, the present invention provides the following.

≪ 1 > A coloring composition comprising a pigment multimer represented by the general formula (1) and a polymerizable compound;

P- (Q) _n ... (One)

In the general formula (1), P represents an n-valent linking group,

Q represents a polymer chain containing a repeating unit having a dye structure,

the average value of the number of n repeating units having a dye structure of Q is 2 or more,

n represents an integer of 3 to 10;

&Lt; 2 > A coloring composition according to < 1 >, wherein the colorant multimer represented by the general formula (1) is represented by the general formula (2);

[Chemical Formula 1]

In the general formula (2), A ¹ represents an n-valent linking group,

B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR-,

R represents a hydrogen atom, an alkyl group or an aryl group,

C ¹ represents a single bond or a divalent linking group,

S represents a sulfur atom,

Q represents a polymer chain containing a repeating unit having a dye structure,

the average value of the number of n repeating units having a dye structure of Q is 2 or more,

n represents an integer of 3 to 10;

<3> A ¹ is an aliphatic hydrocarbon group which may have an oxygen atom in its main chain, aromatic ring group and a group consisting of one or two or more selected from the heterocyclic group in combination, the coloring composition according to <2>.

<4> The coloring composition according to any one of <1> to <3>, wherein the colorant multimer has a specific absorption at a maximum absorption wavelength of 400 nm to 800 nm represented by the following formula (Aλ)

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 multimer in the solution in units of mg / ml.

&Lt; 5 > The coloring composition according to any one of < 1 > to < 4 >, wherein the coloring composition contains 1 to 50 mass% of a pigment multimer relative to the total solid content.

<6> The coloring composition according to any one of <1> to <5>, wherein the pigment multimer is obtained by radical polymerization of a compound represented by the general formula (3) and a compound having a pigment structure and a radically polymerizable group.

P ⁰ - (SH) _n ... (3)

In the general formula (3), P ⁰ represents a linking group of n,

SH represents a thiol group,

n represents an integer of 3 to 10;

<7> The coloring composition according to any one of <1> to <6>, further comprising a colorant other than a colorant multimer.

<8> The coloring composition according to any one of <1> to <7>, which further comprises a photopolymerization initiator.

The Q may be at least one selected from the group consisting of a triarylmethane dye, a xanthine dye, an anthraquinone dye, a cyanine dye, a squarylium dye, a quinophthalone dye, a phthalocyanine dye, a subphthalocyanine dye, The coloring composition according to any one of < 1 > to < 8 >, wherein the coloring composition has a pigment structure derived from a coloring matter selected from pyromethene coloring matter.

<10> The coloring composition according to any one of <1> to <9>, wherein Q has at least one kind selected from repeating units having an acid group and repeating units having a polymerizable group.

<11> The coloring composition according to any one of <1> to <10>, wherein Q is a member selected from the group consisting of a (meth) acrylic resin, a styrene resin and a (meth) acrylic / styrene resin.

<12> A color filter comprising the coloring composition according to any one of <1> to <11>.

&Lt; 13 > A process for producing a colored composition, comprising the steps of: applying a coloring composition according to any one of < 1 > And developing and removing the unexposed portion of the colored composition layer to form a colored pattern.

&Lt; 14 > A process for producing a colored layer, comprising the steps of: applying a coloring composition according to any one of < 1 > to < 11 > onto a support to form a coloring composition layer and curing to form a colored layer; A step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and a step of dry-etching the colored layer using the resist pattern as an etching mask to form a colored pattern.

&Lt; 15 > A method for producing a color filter, comprising the pattern formation method according to < 13 > or < 14 >.

<16> A solid-state image pickup element having a color filter obtained by the color filter according to <12> or the method of manufacturing a color filter according to <15>.

<17> An image display apparatus having a color filter according to <12> or a color filter obtained by the method for manufacturing a color filter described in <15>.

<18> A process for producing a colorant multimer, which comprises radical polymerization of a compound represented by the general formula (3) and a compound having a pigment structure and a radically polymerizable group.

P ⁰ - (SH) _n ... (3)

In the general formula (3), P ⁰ represents a linking group of n,

SH represents a thiol group,

n represents an integer of 3 to 10;

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a colored composition excellent in light resistance, flame retardancy and flatness. It is also possible to provide a color filter, a pattern forming method, a method of manufacturing a color filter, a solid-state image pickup device, an image display device, and a method of producing a dye multimer.

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 those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, light means an actinic ray or radiation. The term " actinic ray " or " radiation " means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray.

In the present specification, unless otherwise specified, the term " exposure " means not only exposure by a bright line spectrum of a mercury lamp, deep ultraviolet ray represented by an excimer laser, X-ray or EUV light, Is included in the exposure.

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.

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

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 reduced values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H , 6.0 mm ID x 15 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

<Coloring composition>

The coloring composition of the present invention contains a pigment multimer represented by the following general formula (1) and a polymerizable compound.

By using the above-described constitution, it is possible to provide a colored composition excellent in light resistance, flame retardancy and flatness.

The reason why such an effect is obtained is not clarified yet, but the dye multimer represented by the general formula (1) to be described later has n polymer chains containing a repeating unit having a dye structure bonded to n connecting groups , It is considered that the entanglement between the polymer chains having the dye structure can be reduced as compared with the dye chain polymer having the linear chain structure. As a result, it is considered that the pigment multimer is hardly aggregated and a film having excellent flatness can be obtained. Further, since the dye structure is introduced into the polymer chain, it is considered that the dye is difficult to diffuse and also excellent in dye transferability. In addition, it is considered that by making the pigment a large amount, adsorption ability with other molecules such as a pigment is improved, and energy transfer between molecules is easy to occur, so that the light resistance is also excellent.

Further, in the case of forming a pattern by photolithography, for example, the entanglement of the polymer chains having the dye structure can be reduced, so that the penetration of the developer can be improved, the developing speed is fast, It may be difficult to do. Hereinafter, the present invention will be described in detail.

&Quot; The pigment represented by the general formula (1) &quot;

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

It is preferable that the maximum absorption wavelength of the dye oligomer (A) is in the range of 400 nm to 800 nm. The colorant oligomer (A) functions as, for example, a coloring agent in the coloring composition of the present invention.

P- (Q) _n ... (One)

In the general formula (1), P represents an n-valent linking group,

Q represents a polymer chain containing a repeating unit having a dye structure,

the average value of the number of n repeating units having a dye structure of Q is 2 or more,

n represents an integer of 3 to 10;

<<< Connector P >>>

In the general formula (1), P represents a linking group of n.

The linking group of n is preferably an alkylene group having 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 Or a sulfur atom, and may be unsubstituted or may further have a substituent.

The linking group represented by P represents an oxygen atom having 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 Lt; / RTI &gt; 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 Of the 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 Of the sulfur atom.

The n-valent linking group represented by P is preferably a linking group derived from a polyhydric alcohol.

In the present invention, the dye multimer represented by the general formula (1) is preferably represented by the general formula (2).

(2)

In the general formula (2), A ¹ represents an n-valent linking group,

B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR-,

R represents a hydrogen atom, an alkyl group or an aryl group,

C ¹ represents a single bond or a divalent linking group,

S represents a sulfur atom,

Q represents a polymer chain containing a repeating unit having a dye structure,

the average value of the number of n repeating units having a dye structure of Q is 2 or more,

n represents an integer of 3 to 10;

The structure of the formula (2a) shown below except for Q in the formula (2) corresponds to the connecting group P in the formula (1). * Denotes the position of coupling with Q.

(3)

In the general formula (2), A ¹ represents an n-valent linking group.

The n-valent linking group is preferably a group consisting of one kind or a combination of two or more kinds selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain.

Examples of the aliphatic hydrocarbon group include an alkylene group and an alkenylene group. The number of carbon atoms of the alkylene group is, for example, preferably from 1 to 60, more preferably from 1 to 30. The carbon number of the alkenylene group is preferably, for example, 1 to 60, more preferably 1 to 30.

Examples of the aliphatic hydrocarbon group having an oxygen atom in the main chain include groups represented by - (OR ^x1 ) _m - and - (R ^x1 O) _m -. The aliphatic hydrocarbon group having an oxygen atom in the main chain may be linear, branched or cyclic. The backbone refers to a skeleton of a linking group and does not include a substituent.

R ^x1 represents an alkylene group or an alkenylene group. m represents an integer of 1 or more, and when m is 2 or more, m R ^x1 may be the same or different.

The alkylene group represented by R ^x1 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. The alkylene group may be linear, branched or cyclic.

The number of carbon atoms of the alkenylene group represented by R ^x1 is preferably from 2 to 20, more preferably from 2 to 10, and still more preferably from 2 to 5. The alkenylene group may be linear, branched or cyclic.

The aromatic ring may be monocyclic or polycyclic. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a chrysene ring, a triphenylene ring, a fluorene ring and a biphenyl ring, and a benzene ring is preferable.

The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be monocyclic or polycyclic. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom. Nitrogen atoms are preferred. The number of heteroatoms is preferably 1 to 3. The heterocycle includes, for example, cyanuron, triazine, oxazine, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine A pyridazin ring, an indolizin ring, an indole ring, a benzofuran ring, a benzothiophen ring, an isobenzofuran ring, a quinolin ring, a quinoline ring, a phthalazin ring, a naphthyridine ring, a quinoxaline ring, A phenanthrene ring, a phenanthrene ring, a phenanthroline ring, a thianthrene ring, a cromene ring, a zentylene ring, a phenoxathiine ring, a phenothiazine ring, a phenanthrene ring, , Triazine ring, oxane ring are preferable.

The n-valent linking group represented by A ¹ is preferably a hydrocarbon group having an oxygen atom in its main chain, an aromatic ring group, a heterocyclic group, a combination of a hydrocarbon group and an aromatic ring group which may have an oxygen atom in the main chain, And a combination of a hydrocarbon group and a heterocyclic group to be used.

A ¹ represents a linking group P in the case of a combination of an aromatic ring, a heterocyclic group, a combination of a hydrocarbon group and an aromatic ring group which may have an oxygen atom in the main chain, or a hydrocarbon group and a heterocyclic group which may have an oxygen atom in the main chain, (2a) may be, for example, the following.

[Chemical Formula 4]

In the formulas, X represents a hydrocarbon group which may have an oxygen atom in its main chain,

B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR-,

R represents a hydrogen atom, an alkyl group or an aryl group,

C ¹ represents a single bond or a divalent linking group,

S represents a sulfur atom,

n represents an integer of 3 or more,

* Denotes the position of coupling with Q.

In the general formula (2), B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR- And is preferably a single bond, -O-, -CO-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-.

R represents a hydrogen atom, an alkyl group or an aryl group.

The number of carbon atoms of the alkyl group represented by R is preferably from 1 to 30, more preferably from 1 to 10. The alkyl group may be linear, branched or cyclic.

The carbon number of the aryl group represented by R is preferably from 6 to 30, more preferably from 6 to 12.

R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

In the general formula (2), C ¹ represents a single bond or a divalent linking group.

As the divalent linking group, an alkylene group, an arylene group, and an oxyalkylene group are preferable, and an alkylene group or an oxyalkylene group is more preferable.

The number of carbon atoms of the alkylene group and the oxyalkylene group is preferably from 1 to 30, more preferably from 1 to 10. The alkyl group and oxyalkylene group may be any of linear, branched and cyclic.

The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 12.

Specific examples of the linking group of n represented by P are shown below. However, the present invention is not limited thereto.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

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

<<< polymer chain Q >>>

The polymer chain represented by Q represents a polymer chain containing a repeating unit having a dye structure, and the average value of the number of repeating units having a pigment structure of n Q is two or more. For n Qs contained in the general formula (1) or (2), two or more repeating units having a dye structure are contained per one Q. The dye multimer represented by the general formula (1) or (2) contains 2n or more repeating units having a pigment structure. The n number of Qs may be the same or different.

The polymer chain represented by Q preferably has an average value of repeating units having a dye structure of 2 to 20, more preferably 2 to 15, and still more preferably 2 to 10.

The average value of the number of repeating units having a dye structure can be determined by NMR (nuclear magnetic resonance). Specifically, for example, the number of repeating units in the general formula (1) is determined from the peak area ratio of the repeating unit of the polymer chain Q and the linking group of the n-valence represented by P. Next, the number of repeating units in the polymer chain Q can be calculated by dividing the value by n.

The weight average molecular weight of the polymer chain Q is preferably 1,000 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

The dye structure of each repeating unit may be the same dye structure or the same skeleton but may be a dye structure having a different substituent or a central metal or a dye structure having a different skeleton.

When the dye structure has a cation and an anion, the cation and the anion may be in the same molecule of the dye structure of the polymer chain Q or may be outside the molecule of the dye structure. Also, having a cation and an anion in the same molecule of the dye structure means a case in which a cation and an anion are bonded through a covalent bond. In addition, the term "having an anion outside the molecule of the dye structure" means that the cation and the anion are not bonded through a covalent bond and exist as separate compounds. Hereinafter, the anion outside the molecule of the dye structure is also referred to as a counter anion.

The polymer chain represented by Q is not particularly limited as long as it contains a dye structure, but it is preferably one selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin.

The (meth) acrylic resin means a resin containing a (meth) acrylic resin as a main component. (Meth) acrylic resin as a main component means that the (meth) acrylic resin preferably contains 50 mass% or more of (meth) acrylic resin, more preferably 60 mass% or more, more preferably 70 mass% or more Is particularly preferable.

The styrene-based resin means a resin containing a styrene resin as a main component. The term "containing styrene resin as a main component" means that the styrene resin preferably contains 50 mass% or more of styrene resin, more preferably 60 mass% or more, and particularly preferably 70 mass% or more .

The (meth) acrylic / styrene resin means a resin containing a (meth) acrylic resin and a styrene resin as main components. (Meth) acrylic resin and styrene resin as the main component means that the (meth) acrylic / styrene resin preferably contains 50 mass% or more of the total of (meth) acrylic resin and styrene resin, and 60 mass% Or more, more preferably 70 mass% or more.

Hereinafter, the polymer chain Q will be described in detail.

<<<< Skeletal structure of repeating unit with pigment structure >>>>

(A), the general formula (B), and the general formula (C) shown in paragraphs 0276 to 0304 of Japanese Patent Laid-Open Publication No. 2013-28764 are not particularly limited, but the skeleton structure of the repeating unit having a dye structure is not particularly limited, Is preferably a skeleton of at least one of the structural units represented by formula (D), or a large amount of a dye represented by formula (D). The description of paragraphs 0276 to 0304 of Japanese Laid-Open Patent Publication No. 2013-28764 is incorporated herein by reference.

In the present invention, it is preferable to have a repeating unit represented by the following general formula (a1-1).

The total amount of repeating units having a dye structure in the total repeating units constituting the polymer chain Q is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, still more preferably from 20 to 40 mol% Is more preferable.

[Chemical Formula 8]

In formula (a1-1), Q ¹ represents a trivalent linking group, L ¹ represents a single bond or a divalent linking group, D ¹ represents a dye structure, "*" represents a bond between the main chain .

In the general formula (a1-1), Q ¹ represents a trivalent linking group. Q ¹ is a linking group formed by polymerization, which refers to a moiety that forms a repeating unit corresponding to a main chain formed by a polymerization reaction. In addition, the parts indicated by two " * " are repeat units.

Q ¹ is preferably a linking group represented by any of the following formulas (XX-1) to (XX-24), more preferably a linking group represented by any one of formulas (XX-1) Linking chain represented by (XX-10) to (XX-17), (XX-18) and (XX-19) and (XX-24) represented by More preferably a chain selected from the group consisting of a (meth) acrylic linkage chain represented by (XX-1) and (XX-2), a styrene-based chain represented by (XX- More preferably selected from vinyl-based connecting chains represented by (XX-1) and (XX-2), and more preferably the styrene-based connecting chains represented by (meth) acrylic connecting chains and Do.

(XX-1) to (XX-24), the part indicated by * indicates that it is connected to L ¹ .

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

[Chemical Formula 9]

[Chemical formula 10]

In formula (a1-1), L ¹ independently represents a single bond or a divalent linking group.

Examples of the divalent linking group include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butylene group), a substituted or unsubstituted A substituted or unsubstituted heterocyclic group, -CH = CH-, -O-, -S-, -C (= O) -, -CO ₂ -, or a substituted or unsubstituted arylene group (e.g., a phenylene group or a naphthylene group) _{, -NR-, -CONR-, -O 2 C-} , -SO-, -SO 2 - , and these represent a bonding group formed by linking two or more. It is also preferable that L ¹ contains an anion. L ¹ is preferably a single bond or an alkylene group, more preferably a single bond or - (CH ₂ ) _n - (n is an integer of 1 to 5). Here, R represents, independently of each other, a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

D ¹ represents a dye structure derived from a dye compound to be described later.

<<<< Pigment structure >>>>

The pigment structure is not particularly limited, and various ones including known pigment structures can be applied.

Specific dye compounds capable of forming a pigment structure are described in "New Edition Dye Handbook" (edited by Organic Synthetic Chemistry Association, Maruzen, 1970), "Society of Dyers and colourists", " Kodansha, 1986).

Examples of the colorant include quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes and anthrapyridone dyes), carbonium dyes (diarylmethane dyes, triarylmethane dyes, xanthine dyes, Etc.), quinone imine pigments (oxazine pigments, thiazine pigments, etc.), azine pigments, polymethine pigments (oxolin pigments, merocyanine pigments, aziridene pigments, stearyl pigments, cyanine pigments, squarylium A quinoline dye, a nitroso dye, a nitroso dye, a quinophthalone dye, a phthalocyanine dye, a subphthalocyanine dye, a perinone dye, an indigo dye, a thioindigo dye, A dye structure derived from a dye selected from a dipyramethane dye, an azo dye and a metal complex dye thereof.

Among these dye structures, from the viewpoints of color separation property and light resistance, it is preferable to use at least one of triarylmethane dye, xanthine dye, anthraquinone dye, cyanine dye, squarylium dye, quinophthalone dye, phthalocyanine dye, A dye structure selected from a dyes, a cyanine dyes, an azo dyes and a dipyramethine dyes is preferable, and a dye structure selected from among triarylmethane dyes, xanthine dyes, anthraquinone dyes, squarilium dyes, quinophthalone dyes, phthalocyanine dyes, More preferably a dye structure selected from phthalocyanine dyes, azo dyes and dipyramethine dyes, and more preferably a triarylmethane dye and a xanthine dye. The dye structure contained in the polymer chain represented by Q may be either one kind or two or more kinds.

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

<<<<< Triaryl Methane Pigment >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a triarylmethane dye (triarylmethane compound). Examples of the triarylmethane dye include compounds represented by the following formula (TP). The term "triarylmethane compound" refers to a compound having a dye moiety having a triarylmethane skeleton in its molecule.

Equation (TP)

(11)

In the formula (TP), Rtp ¹ to Rtp ⁴ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp ⁵ 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.

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 substituent represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be any of the substituents described in the Substituent Group A described later. In particular, the substituent may be a linear or branched alkyl group having 1 to 5 carbon atoms, An aryl group, a carboxyl group or a sulfo group having 6 to 15 carbon atoms is preferable, and a straight 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 b are each preferably 0 or 1, and c is preferably an integer of 0 to 2.

When at least one of Rtp ¹ to Rtp ⁷ contains an anion, examples of the anion include a structure in which at least one of Rtp ¹ to Rtp ⁷ is substituted with a general formula (P).

In general formula (P)

[Chemical Formula 12]

In the general formula (P), L represents a single bond or a divalent linking group, X ^{1 _{is, -SO 3 -, -COO -,}} -PO 4 - group to which, comprises a structure represented by the general formula (A1) and Is selected from at least one group selected from the group comprising a structure represented by the following general formula (A2).

In formula (A1)

[Chemical Formula 13]

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

In general formula (A2)

[Chemical Formula 14]

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

In the general formula (P), L represents a single bond or a divalent linking group. The divalent linking group is preferably a group consisting of -NR ¹⁰ -, -O-, -SO ₂ -, a fluorine-substituted alkylene group, a fluorine-substituted phenylene group, or a combination thereof. In particular, a group consisting of a combination of -NR ¹⁰ - and -SO ₂ - and a fluorine-substituted alkylene group, a group formed by a combination of -O- and a fluorine-substituted phenylene group, -NR ¹⁰ - and -SO ₂ - A group formed by a combination of cyanuric groups is preferable.

In -NR ¹⁰ -, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is preferably a hydrogen atom.

The fluorine-substituted alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of the fluorine-substituted alkylene group include a difluoromethylene group, a tetrafluoroethylene group, and a hexafluoropropylene group.

The number of carbon atoms of the fluorine-substituted phenylene group is preferably from 6 to 20, more preferably from 6 to 14, and even more preferably from 6 to 10. Specific examples of the fluorine-substituted phenylene group include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group and a hexafluoro-2-naphthylene group.

In the general formula (P), X ¹ is an anionic, -SO ₃ ^-, -COO ^-, the formula selected from a group containing a structure represented by the group, and general formula (A2) containing a structure represented by (A1) , And the like.

The group containing the structure represented by the general formula (A1) is preferably a fluorine-substituted alkyl group at one of the ends of R ¹ and R ² in the general formula (A1), and one of R ¹ and R ² More preferably a fluorine-substituted alkyl group. The number of carbon atoms of the fluorine-substituted alkyl group is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 1 to 3, still more preferably 1 or 2, These alkyl groups are more preferably perfluoroalkyl groups. As specific examples of the fluorine-substituted alkyl group, a trifluoromethyl group is preferable.

Of the general formula (A2) group containing a structure represented by the above-described general formula (A2), R ³ ~ R in at least one of the ends of the ^5, desirable to have a fluorine-substituted alkyl group, R ³ ~ R ⁵ And it is more preferable that at least two of them are bonded to the fluorine-substituted alkyl group directly. In particular, R ³ ~ R to at least two of the terminal ^5, preferably has a fluorine-substituted alkyl group, more preferably that R ³ ~ R in combination with at least two fluorine-substituted alkyl group of ⁵ directly. The fluorine-substituted alkyl group is the same as that described in the group including the structure represented by formula (A1), and the preferable range is also the same.

<<<<< xanthan color >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a xanthine dye (xanthine compound). As the xanthene dye, a xanthene compound represented by the following formula (J) can be mentioned.

[Chemical Formula 15]

In 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, Lt; / RTI &gt; X ^- represents a counter anion. When X &lt; ^{- &} gt ^; is absent, at least one of R ⁸¹ to R ⁸⁵ includes an anion.

The substituent group R ⁸¹ to R ⁸⁵ in the formula (J) is the same as the substituent group in the group of Substituent Group A described later.

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

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

Examples of the anion include those described above.

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, pages 3097 to 3106 can be applied.

When X ^- represents an anion, reference can be made to a case where the opposite anion 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 opposite anion is present in the same constitutional unit.

Further, among the dye structures, the cations are present on the carbon atom of the nitrogen atom or the zirconium ring, as shown below, for example, since they are non-localized.

[Chemical Formula 16]

<<<<< Anthraquinone color >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from an anthraquinone dye. As the anthraquinone dye (anthraquinone compound), compounds represented by the following general formulas (AQ-1) to (AQ-3) are preferable. An anthraquinone compound is a compound generally referred to as a compound having a dye moiety including an anthraquinone skeleton in a molecule.

[Chemical Formula 17]

In the general formula (AQ-1), A and B each independently represent an amino group, a hydroxyl group, an alkoxy group or a hydrogen atom. And Xqa represents ORqa ¹ or NRqa ² Rqa ³ . Each of Rqa ¹ to Rqa ³ independently represents a hydrogen atom, an alkyl group or an aryl group. Rq ₁ to Rq ₄ represent substituents. The substituents Rq ₁ to Rq ₄ can take are the same as the substituents in the group of Substituent Group A described later. Ra and Rb each independently represent a hydrogen atom, an alkyl group or an aryl group.

In the general formula (AQ-2), C and D are synonymous with A and B in the general formula (AQ-1). And Xqb represents ORqb ¹ or NRqb ² Rqb ³ . Each of Rqb ¹ to Rqb ³ independently represents a hydrogen atom, an alkyl group or an aryl group. Rq Rq ₅ ~ ₈ represents a substituent. Rq ₅ to Rq ₈ are the same as Rq ₁ to Rq ₄ in the general formula (AQ-1). Rc is synonymous with Ra or Rb in formula (AQ-1).

In the general formula (AQ-3), E and F are synonymous with A and B in the general formula (AQ-1). Xqc represents ORqc ¹ or NRqc ² Rqc ³ . Each of Rqc ¹ to Rqc ³ independently represents a hydrogen atom, an alkyl group or an aryl group. Rq Rq ₉ ~ ₁₂ is a Rq Rq ₁ ~ ₄ and the consent of the general formula (AQ-1). Rd is synonymous with Ra or Rb in the general formula (AQ-1).

As a preferable range of the general formulas (AQ-1), (AQ-2) and (AQ-3), for example, see paragraphs 0045 to 0047 of Japanese Patent Laid-Open Publication No. 2013-29760, .

As an anthraquinone dye, for example, refer to paragraphs 0049 to 0050 of Japanese Laid-Open Patent Publication No. 2013-29760, the contents of which are incorporated herein by reference.

<<<<< Cyanine color >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a cyanine dye (a cyanide compound). As the cyanine dye, a compound (cyanide compound) represented by the following general formula (PM) is preferable. In the present invention, a cyanide compound refers to a compound having a dye site including a cyanide skeleton in a molecule.

[Chemical Formula 18]

In the general formula (PM), ring Z1 and ring Z2 each independently represent a heterocyclic ring 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, which is incorporated herein by reference. In the specific example of the cyanine dye described in paragraphs 0077 to 0084 of Japanese Laid-Open Patent Publication No. 2013-29760, any one hydrogen atom of the cyanine dye structure binds to R ² of the general formula (1).

<<<<< Squarylium pigment >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a squarylium dye (squarylium compound). As the squarylium dye, a compound represented by the following 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 or a heterocyclic group. 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 pyrroyl, imidazoyl, pyrazolyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol- Thia diamonds, and the like.

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

As a specific example of the squarylium dye, see, for example, paragraph 0105 of Japanese Laid-Open Patent Publication No. 2013-29760.

<<<<< Quinofthalone color >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a quinophthalone dye (quinophthalone compound). As the quinophthalone dye, a compound represented by the following general formula (QP) (quinophthalone compound) is preferable. The quinophthalone compound in the present invention refers to a compound having a dye moiety having a quinophthalone skeleton in its molecule.

[Chemical Formula 20]

In the general formula (QP), each of Rqp ₁ to Rqp ₆ independently represents a hydrogen atom or a substituent. When at least two of Rqp ₁ to Rqp ₆ are adjacent to each other, they may be bonded to each other to form a ring, and the ring formed may further have a substituent.

As a preferable range of the general formula (QP), for example, see paragraphs 0110 to 0114 of Japanese Laid-Open Patent Publication No. 2013-29760, which is incorporated herein by reference.

As a specific example of the quinophthalone dye, reference can be made, for example, to paragraph 0113 of Japanese Laid-Open Patent Publication No. 2013-29760.

<<<<< phthalocyanine color >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a phthalocyanine dye (phthalocyanine compound). The phthalocyanine dye preferably has a partial structure derived from a compound represented by the following general formula (F) (phthalocyanine compound). The phthalocyanine compound in the present invention refers to a compound having a pigment moiety including a phthalocyanine skeleton in a molecule.

[Chemical Formula 21]

In Formula (F), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a hydrogen atom, an atom selected from a hydrogen atom, a carbon atom, Represents the group of atoms necessary to form a ring.

As a preferable range of the general formula (F), reference may be made, for example, to paragraphs 0118 to 0124 of Japanese Laid-Open Patent Publication No. 2013-29760, the contents of which are incorporated herein by reference.

As specific examples of phthalocyanine pigments, see, for example, Japanese Patent Application Laid-Open No. 2013-29760, paragraph 0123.

<<<<< Subphthalocyanine pigment >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a subphthalocyanine dye (subphthalocyanine compound). As the subphthalocyanine dye, a compound represented by the following general formula (SP) (a subphthalocyanine compound) is preferable. In the present invention, a subphthalocyanine compound refers to a compound having a dye moiety including a subphthalocyanine skeleton in a molecule.

[Chemical Formula 22]

In formula (SP), Z ¹ to Z ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amino group, an alkoxy group, an aryloxy group or a thioether group. X represents an anion.

As a preferable range of the general formula (SP), for example, reference can be made to paragraphs 0128 to 0133 of Japanese Laid-Open Patent Publication No. 2013-29760, the contents of which are incorporated herein by reference.

As a specific example of the subphthalocyanine dye, for example, reference may be made to paragraph 0132 of Japanese Laid-Open Patent Publication No. 2013-29760.

<<<<< Azo dye >>>>>

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from an azo dye (azo compound). In the present invention, an azo compound generally refers to a compound having a dye moiety containing N = N groups in a molecule. The azo dye can be appropriately selected from known azo dyes (for example, substituted azo benzene). For example, as the azo dye, reference can be made to the description of paragraphs 0084 to 0134 of Japanese Laid-Open Patent Publication No. 2013-41097 and the description of paragraphs 0029 to 0136 of Japanese Laid-Open Patent Publication No. 2011-162760, Is used.

<<<<< Dipyromethane coloring >>>>>

One embodiment of the dye structure according to the present invention is one having a partial structure derived from a dipyramethane dye. As the dipyrammethene dye, a dipyrammethene compound and a dipyrammethene metal complex compound obtained from a dipyrammethene compound and a metal or a metal compound are preferable. For example, as the dipyrammethene dye, reference can be made to the description of paragraphs 0033 to 0136 of Japanese Laid-Open Patent Publication No. 2011-95732, the content of which is incorporated herein by reference.

The hydrogen atom in the dye structure may be substituted with a substituent selected from Substituent Group A below.

(Substituent group A)

Examples of the substituent which the dye structure may have 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, Branched or cyclic alkyl group and is, for example, methyl, ethyl, propyl, isopropyl, butyl (preferably t-butyl), pentyl, hexyl, heptyl, octyl, (Preferably an alkenyl group having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, (Preferably having from 2 to 20 carbon atoms, more preferably from 2 to 12 carbon atoms, particularly preferably from 2 to 8 carbon atoms, such as, for example, vinyl, allyl and 3-butene- , 3-pentanyl and the like), an aryl group (preferably having 6 to 48 carbon atoms, more preferably 6 carbon atoms (For example, phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol- Is a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl) An alkoxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, Butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy), aryloxy groups (For example, phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably 1 to 20 carbon atoms, Is a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (preferably having 1 to 32 carbon atoms, (For example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably having 2 to 48 carbon atoms, more preferably a carbon number An alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy) Alkoxycarbonyloxy group, for example ethoxycarbonyloxy, t-butoxycarbonyloxy , A cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably a carbon number 7 to 24, For example, phenoxycarbonyloxy),

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) A phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphine oil amino group (Preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, For example, diethoxyphosphine oil amino, dioctyloxyphosphine oil amino), an alkyloxycarbonyloxy group (preferably an alkyloxycarbonyloxy group having 5 to 30 carbon atoms, more preferably 5 to 10 carbon atoms ) 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, reference may be made, for example, to paragraphs 0027 to 0038 of Japanese Laid-Open Patent Publication No. 2013-29760, the contents of which are incorporated herein by reference.

<<<< The opposite negative ion >>>>

When the dye structure is composed of a cation and a counter anion, the counter anion is not particularly limited, but from the viewpoint of heat resistance, it is preferable that the anion is an anion. As the counter anion of the non-nucleophilic nature, a known non-nucleophilic anion described in JP-A-2007-310315, paragraph No. 0075 is preferable. Here, the term &quot; non-nucleophilic &quot; means a property of not attacking the pigment by nucleation.

As the counter anion, 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 them, as the counter anion, an unconjugated anion having a structure represented by the following (AN-1) to (AN-5) is more preferable.

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

&Lt; EMI ID =

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

X ³ , X ⁴ and X ⁵ are, each independently, 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 preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.

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

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

The counter anion of the non-nucleophilic group may also be -B (CN) _n1 (OR ^a ) _4-n1 wherein R ^a is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, n1 is an integer of 1 to 4 ). R ^a as an alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R ^a as an aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.

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

The counter anion of the non-nucleophilic group is also preferably -PF ₆ R ^P _{(6-n 2)} ^- (wherein R ^P is a fluorinated alkyl group having 1 to 10 carbon atoms and n 2 is an integer of 1 to 6). R ^P is preferably an alkyl group having a fluorine atom of 1 to 6 carbon atoms, more preferably an alkyl group having a fluorine atom of 1 to 4 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

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

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

The colorant oligomer (A) may contain only one kind of non-nucleophilic counter anion or two or more kinds of non-nucleophilic counter anions.

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

(28)

[Chemical Formula 29]

(30)

(31)

Specific examples of the repeating unit having a pigment structure, which is preferably used in the present invention, are shown below. It is needless to say that the present invention is not limited to these.

(32)

(33)

(34)

<<<< Other Repeat Units >>>>

The polymer chain Q may contain a repeating unit other than the above-described repeating unit having a dye structure. The other repeating unit may contain a functional group such as a polymerizable group and an acid group. It may not contain a functional group. A repeating unit having an acid group and a repeating unit having a polymerizable group, and more preferably a repeating unit having an acid group.

As the polymerizable group, known polymerizable groups capable of crosslinking by radicals, acids and heat can be used, and examples thereof include groups containing ethylenic unsaturated bonds, cyclic ethers (epoxy groups, oxetane groups), methylol groups And a group containing an ethylenically unsaturated bond is preferable, and a (meth) acryloyl group is more preferable. The (meth) acryloyl group can be introduced, for example, by reacting glycidyl (meth) acrylate with 3,4-epoxycyclohexylmethyl (meth) acrylate.

When the polymer chain Q comprises a repeating unit having a polymerizable group, the proportion of the repeating unit having a polymerizable group is preferably 5 to 50 moles, more preferably 10 to 40 moles per 100 moles of the total repeating units of the polymer chain Q, The molar amount is more preferable.

Examples of the acid group include a carboxyl group, a sulfonic acid group and a phosphoric acid group. The acid group may be contained only in one kind or in two or more kinds.

When the polymer chain Q contains a repeating unit having an acid group, the proportion of the repeating unit having an acid group is preferably 5 to 50 moles, more preferably 10 to 40 moles, per 100 moles of the total repeating units of the polymer chain Q desirable.

Examples of the other functional groups include a repeating group of 2 to 20 unsubstituted alkyleneoxy chains, a development promoter such as a lactone group, an acid anhydride group, an amide group and a cyano group, a long chain and cyclic alkyl group, an aralkyl group, , A polyalkylene oxide group, a hydroxyl group, a maleimide group, and an amino group, and the like, and they can be suitably introduced.

In the group consisting of repetition of 2 to 20 unsubstituted alkyleneoxy chains, the number of repeating alkyleneoxy chains is preferably 2 to 10, more preferably 2 to 15, and even more preferably 2 to 10 . One alkyleneoxy group is represented by - (CH ₂ ) _n O- and n is an integer, and n is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 or 3.

Specific examples of other repeating units are shown, but the present invention is not limited thereto.

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(36)

(37)

<<< Polymeric chain not containing pigment structure >>>

The colorant oligomer (A) may have a polymer chain not containing a dye structure.

Examples of the polymer chain not including the dye structure include a polymer chain composed of repeating units described in other repeating units of the polymer chain Q described above.

<< Properties of pigment multimer (A) >>

The weight average molecular weight of the colorant oligomer (A) is preferably 1000 to 100000. The lower limit is, for example, more preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more. The upper limit is more preferably 50000 or less, more preferably 20000 or less, and even more preferably 15000 or less. If the weight average molecular weight is in the above range, the dyeing property is better. Further, the developability is improved, and the occurrence of the development residue can be further reduced.

The acid value of the colorant oligomer (A) is preferably 10 mgKOH / g or more. The lower limit is more preferably 15 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit is more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less. When the acid value is 10 mgKOH / g or more, the developability is improved and the occurrence of the development residue can be further reduced.

The non-absorbance of the colorant multimer (A) can be measured, for example, by using a solvent having sufficient solubility to the colorant multimer (A) to obtain a colorant oligomer (A) having a maximum absorbance at 400 nm to 800 nm of 1.0 ), And measuring the absorbance of the 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 the colorant multimer (A) 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 following formula (A?) At a maximum absorption wavelength in the range of 400 nm to 800 nm is preferably 5 or more, more preferably 10 or more, further preferably 20 or more, and particularly preferably 30 or more. When the specific absorbance is 5 or more, it can be suitably used as a coloring agent.

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 multimer in the solution in units of mg / ml.

The dye-sensitized compound (A) is preferably a dye. The dye is a dye which has a substantial solubility in water or an organic solvent, and is preferably an organic solvent soluble dye soluble in the following organic solvent.

Examples of the organic solvent include esters (e.g., methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate and methyl 3-methoxypropionate), ethers Acetone, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3- , And aromatic hydrocarbon (for example, toluene, xylene, etc.). The solvent is preferably dissolved in an amount of 1 to 50 mass%, more preferably 5 to 40 mass% And particularly preferably 10 to 30% by mass. Within this range, when the coloring composition of the present invention is applied to the production of a color filter or the like, the shape of the coated surface becomes suitable, and the concentration lowering due to elution after coating with other colors can be further reduced.

In the coloring composition of the present invention, the colorant oligomer (A) may be used singly or in combination of two or more.

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

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

The content of the colorant multimer (A) in the coloring composition of the present invention is preferably from 1 to 50 mass%, more preferably from 5 to 30 mass%, and still more preferably from 10 to 25 mass%, based on the total solid content of the coloring composition Particularly preferred.

&Lt; Synthesis method of dye multimer (A) &gt;

The method for producing the colorant multimer represented by the above general formula (1) is not particularly limited, but a multifunctional thiol compound having 3 to 10 thiol groups per molecule and a compound having a pigment structure and a radical polymerizable group are reacted with a radical Followed by polymerization. Hereinafter, the compound having a pigment structure and a radically polymerizable group is also referred to as a " radically polymerizable dye compound ".

As the pigment structure in the radical polymerizable coloring matter compound, the above-mentioned ones can be mentioned. In the radical polymerizable dye compound, examples of the radically polymerizable group include groups containing an ethylenic unsaturated bond such as a vinyl group, (meth) allyl group, or (meth) acryloyl group.

More specifically, a method of radically polymerizing a compound represented by the general formula (3) and a radical polymerizable dye compound is preferred.

P ⁰ - (SH) _n ... (3)

In the general formula (3), P ⁰ represents a linking group of n,

SH represents a thiol group,

n represents an integer of 3 to 10;

In the general formula (3), P ⁰ represents an alkyl group having 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms , And a group consisting of 0 to 20 sulfur atoms, which may be unsubstituted or may further have a substituent.

The linking group represented by P &lt; ⁰ &gt; may have from 1 to 60 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 40 oxygen atoms, from 1 to 120 hydrogen atoms, and from 0 Groups consisting of up 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 Of the 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 Of the sulfur atom.

The n-valent linking group represented by P ⁰ is preferably a linking group derived from a polyhydric alcohol.

The compound represented by the general formula (3) is preferably the compound represented by the general formula (4).

A ⁰ - (B ⁰ -C ⁰ -SH) _n - (4)

In the general formula (4), A ⁰ represents a linking group of n,

B ⁰ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR-,

R represents a hydrogen atom, an alkyl group or an aryl group,

C ⁰ represents a single bond or a divalent linking group,

SH represents a thiol group,

n represents an integer of 3 to 10;

A ⁰ , B ⁰ and C ⁰ in the general formula (4) are in agreement with the ranges described for A ¹ , B ¹ and C ¹ in the general formula (2), respectively, and preferred embodiments are also the same.

Specific examples of the compound represented by the general formula (3) include the following compounds.

(38)

[Chemical Formula 39]

(40)

Among these, particularly preferred compounds are (SH-1) to (SH-8), (SH-16) to (SH-20), (SH-22) to (SH-32) are preferable.

The radical polymerization of the polyfunctional thiol compound and the radical polymerizable dye compound can be carried out, for example, by dissolving the polyfunctional thiol compound and the radical polymerizable dye compound in an appropriate solvent, adding a radical generator thereto, At a temperature of from room temperature to 100 ° C (thiol-ene reaction method).

Examples of a suitable solvent to be used in the thiol-ene reaction method may be arbitrarily selected depending on the solubility of the polyfunctional thiol compound and the radical polymerizable dye compound.

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.

<< Polymerizable compound >>

The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, known compounds that can be crosslinked by radicals, acids and heat can be used. For example, a compound having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group, or the like can be given. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. In the present invention, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 6 functional groups.

The polymerizable compound may be, for example, a monomer, a prepolymer (i.e., a dimer, a trimer and an oligomer), or a mixture thereof and a chemical form thereof such as a multimer thereof.

Examples of monomers and prepolymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and oligomers thereof , 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, and a multimer 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 at least one group having an ethylenic unsaturated bond and a boiling point of at least 100 캜 at normal pressure. As an example thereof, reference may be made to the compounds described in paragraphs 0227 and 02257 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970, the contents of which are incorporated herein by reference.

As the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kayaku Co., Ltd., (KAYARAD D-310 manufactured by Nippon Kayaku Kabushiki Kaisha), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Kabushiki Kaisha), dipentaerythritol penta A-DPH-12E manufactured by Shin-Nakamura Kagaku Co., Ltd.), and a structure in which the (meth) acryloyl group intervenes between ethylene glycol and propylene glycol moieties (for example, SR454, SR499, which are commercially available, for example). These oligomer types can also be used. 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. The polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably an ester in which an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a nonaromatic carboxylic acid anhydride to give an acid group 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 made by Toagosei Co., Ltd.

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

As the polymerizable compound, a compound having a structure derived from a cyclic ester (e.g., caprolactone, valerolactone and the like, caprolactone being particularly preferable) is also a preferable embodiment.

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

(41)

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).

(42)

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

(43)

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

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

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

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

In the general formula (Z-4), the sum of the (meth) acryloyl groups 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. 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 (meth) acryloyl groups is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60. 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- Side 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 obtained by a process comprising the steps of: coupling a ring opening skeleton to pentaerythritol or dipentaerythritol by ring-opening addition reaction of ethylene oxide or propylene oxide; Can be synthesized from a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride to the terminal hydroxyl group of the terminal hydroxyl group. 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) are examples of the compounds represented by the following formulas , (e) and (f) are preferable.

[Chemical Formula 45]

(46)

Examples of commercially available products of the polymerizable compounds represented by the general formula (Z-4) or (Z-5) include SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having 6 pentylene oxy chains, TPA-330, which is a trifunctional acrylate having three isobutylene oxy chains, and the like.

In the present invention, as the polymerizable compound, a compound having an epoxy group may also be used. 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.

The compound having an epoxy group in the present invention is preferably a compound having a structure in which two benzene rings are connected to each other through hydrocarbon groups. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.

The epoxy group is preferably connected through a linking group. Examples of the linking group include a structure represented by an alkylene group, an arylene group, -O-, -NR'- (wherein R 'represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent and preferably a hydrogen atom) -SO ₂ -, -CO-, -O-, and -S-.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of a compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, further preferably 100 to 300 g / eq Do. The above effect can be obtained by setting the upper limit of the epoxy equivalent of the epoxy group-containing compound to 500 g / eq or less. The lower limit of the epoxy equivalent of a compound having an epoxy group is preferably 100 g / eq or more in view of practical stability.

The compound having an epoxy group may be a low molecular weight compound (for example, having a molecular weight of less than 2000, and further having a molecular weight of less than 1000), and may be a macromolecule (for example, a molecular weight of 1000 or more, 1000 or more). The weight-average molecular weight of the compound having an epoxy group is preferably 200 to 100000, more preferably 500 to 50,000.

As the compound having an epoxy group in the structure in which two benzene rings are connected to each other through a hydrocarbon group, a compound represented by the following formula (2a) is preferably used.

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In formula (2a), R ¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.

For details of R ¹ to R ^{19 in} the general formula (2a), reference may be made to paragraph No. 0036 of Japanese Laid-Open Patent Publication No. 2013-011869, the contents of which are incorporated herein by reference.

In particular, each of R ¹ to R ¹⁹ is preferably independently a hydrogen atom, a methyl group, an ethyl group or a methoxy group. More preferably, at least one selected from R ¹³ , R ¹⁸ and R ¹⁹ is a methyl group. More preferably, R ¹³ , R ¹⁸ and R ¹⁹ are methyl groups, and R ¹ to R ¹² and R ¹⁴ to R ¹⁷ are hydrogen atoms.

The compound represented by the above general formula (2a) can be synthesized by referring to Japanese Patent Application Laid-Open No. 2013-011869, Paragraph No. 0036. Commercially available products include VG-3101L manufactured by Takeuchi Chemical Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd., and the like.

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

(48)

In the formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group may have a cyclic structure or may have a substituent. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure.

Q ^EP represents an organic group of single bond or n ^EP . R ^EP1 to R ^EP3 may also be bonded to Q ^EP to form a ring structure.

n ^EP represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. However, when Q ^EP is a single bond, n ^EP is 2.

For details of R ^EP1 to R ^EP3 and Q ^EP , reference can be made to the description of paragraphs 0087 to 0088 of Japanese Laid-Open Patent Publication No. 2014-089408, the contents of which are incorporated herein by reference.

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

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As the compound having an epoxy group, an oligomer or polymer having an epoxy group in the side chain can also be preferably used. Examples of such a compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an aliphatic epoxy resin.

These compounds may be commercially available products or may be obtained by introducing an epoxy group into the side chain of the polymer.

As commercial products, for example, bisphenol A type epoxy resins include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), and the like. Examples of the bisphenol F type epoxy resin include JER806, JER807, JER4004, JER4005, JER4007, JER4010 JER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy Resin Co., Ltd.), and the like can be used as the phenol novolak type epoxy resin, (EPICLON N-660, EPICLON N-665, EPICLON N-775, and EPICLON N-775 manufactured by DIC Corporation) EPICLON N-690, EPICLON N-690, EPICLON N-690 (manufactured by DIC Corporation) and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) in (Manufactured by ADEKA Corporation), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600, and EPOLEAD PB 3600, which are manufactured by ADEKA RESIN EP-4080S, EP- PB 4700 (manufactured by Daicel Chemical Industries Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L and EX-850L (manufactured by Nagase ChemteX Corporation) . 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 DIC Corporation), EPICLON 840 (manufactured by Mitsubishi Kagaku K.K.), JER1032H60 (Manufactured by DIC Corporation), EPICLON N660 (manufactured by DIC Corporation), and EPICLON HP7200 (manufactured by DIC Corporation).

In the present invention, polymeric compounds are described in Japanese Examined Patent Publication Nos. 48-41708, 51-37193, 2-32293, and 2-16765, Butene-containing acrylate, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, Yutein compounds having an oxide-based skeleton are also suitable. Further, addition polymerizable compounds having an amino structure or sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238, , A coloring 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. Examples of compounds having oxetecyl groups include 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 and PNOX (manufactured by Doago Kosai Co., Ltd.) can be used.

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

In the coloring composition of the present invention, the content of the polymerizable compound is preferably from 0.1 to 30% by mass relative to the total solid content of the coloring composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 20 mass% or less, for example, and further preferably 15 mass% or less. The polymerizable compounds may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount is 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)

(51)

(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.

(52)

When the coloring composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol is preferably 0.3 to 8.9 mass%, more preferably 0.8 to 6.4 mass%, based on the total solid content of the coloring composition. The polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability and adhesion.

<< Other color >>

The coloring composition of the present invention may contain a coloring matter other than the above-mentioned colorant multimer (A) (hereinafter, also referred to as another coloring matter). The other pigments are preferably pigments because they can be favorably used for both pigments and dyes and have high resistance to heat and light.

The content of the pigment in the other pigments is preferably 95% by mass or more, more preferably 97% by mass or more, further preferably 99% by mass or more based on the total amount of the other pigments. According to this embodiment, the effect of increasing the resistance to heat and light is easily obtained.

As the pigment, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferred.

<<< Dye >>>

The dye is not particularly limited, and known dyes used in color filters can be used. For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301, 6-11614, 2592207, 4808501, US 5667920, US 505950, US 5667920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And JP-A-6-194828 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.

<<< Pigment >>>

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, 167, 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.

The organic pigments may be used alone or in various combinations in order to adjust the spectroscopy or increase the color purity. Specific examples of preferable combinations are shown below.

Examples of the red pigment include an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isophorone yellow pigment, a quinophthalone pigment, A yellow pigment, a perylene red pigment, or the like can be used. Examples of the anthraquinone pigments include CI Pigment Red 177, and the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224. As the diketopyrrolopyrrole pigments, CI Pigment Red 254, and it is preferable to mix with CI Pigment Yellow 139 in terms of color degradability. The mass ratio of the red pigment to the yellow pigment is preferably 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 in accordance with the obtained spectroscopy.

As the green pigment, a halogenated phthalocyanine pigment may be used singly or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethan yellow pigment or an isoindolene yellow pigment have. Examples of these include CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, Lt; RTI ID = 0.0 &gt; 185 &lt; / RTI &gt; 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 the black matrix, carbon, titanium black, iron oxide, titanium oxide alone, or a mixture of two or more 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 and contrast. Also, from the viewpoint of dispersion stability, it is preferably 5 nm or more. The primary particle size 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 size of the pigment can be measured by a known method such as an electron microscope.

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

When the coloring composition of the present invention contains other coloring matters, the content of the other coloring matter is preferably 10 to 70 mass%, more preferably 25 to 65 mass%, and more preferably 35 to 55 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 kind of other coloring matter or may contain two or more kinds of other coloring matters. When two or more kinds are included, the total amount is preferably in the above range.

<< Resin >>

The coloring composition of the present invention preferably contains a resin. Examples of the resin include a resin (dispersion resin) for dispersing a pigment and an alkali-soluble resin.

<<< Dispersion resin >>>

As the dispersing resin, there may be mentioned, for example, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) , Naphthalenesulfonic acid-formalin condensate, and the like.

The polymer dispersant is further classified into a block polymer having a linear polymer, an end-modified polymer having an anchor site on the pigment surface, a graft polymer having an anchor site on the pigment surface, and an anchor site on the pigment surface from the structure can do.

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

Examples of the graft-type polymer having an anchor portion to the pigment surface include a polyester-based resin and the like. Specifically, the reaction product of a poly (lower alkyleneimine) and a polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, A reaction product of a polyallylamine and a polyester described in Japanese Patent Application Laid-Open No. 9-169821, a macromonomer described in JP-A No. 10-339949, JP-A No. 2004-37986, etc., a copolymer of a nitrogen atom monomer, Graft polymers having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-2003-238837, JP-A-2008-9426, and JP-A-2008-81732, JP-A-2010-106268 And a copolymer of an acid group-containing monomer and the like. In particular, the amphoteric resin having a basic group and an acid group described in JP-A-2009-203462 is particularly preferable in view of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion .

Known macromonomers can be used as the macromonomer used when the graft polymer is produced by radical polymerization. Macromonomer AA-6 (polymethacryloyl group having a terminal group of methacryloyl group) manufactured by DOKOSEI CO., LTD. , AN-6S (a copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (poly (meth) acrylate having a terminal group of methacryloyl group), AS-6 (polystyrene in which the terminal group is methacryloyl group) Butyl acrylate), Flaccel FM5 (5-molar equivalent of 2-hydroxyethyl methacrylate-epsilon -caprolactone) manufactured by Daicel Chemical Industries, Ltd., FA10L (? -Caprolactone of 2-hydroxyethyl acrylate 10 molar equivalents of lactone), and polyester-based macromonomers described in JP-A-2-272009. Of these, polyester-based macromonomers having particularly good flexibility and good solventability are preferable from the viewpoints of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, and Japanese Laid- Especially preferred are polyester-based macromonomers represented by the polyester-based macromonomers described in JP-A-27-272009.

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

Specific examples thereof include DA-7301 manufactured by Gusumoto Kasei Co., Ltd., Disperbyk-101 (polyamide amine phosphate) manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 Quot; BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ", manufactured by EFKA Co., Ltd.), 130 (polyamide), 161,162,163,164,165,166 (Denatured polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid salt), EFKA4030 to EFKA4030 to EFKA4330 to EFKA4340 to EFKA4340 to EFKA4340 to EFKA4340 to EFKA4340 to EFKA4340 to EFKA4340 to EFKA4340, (Azobisisobutyronitrile), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), Azizuper PB821, PB822, PB880, PB881 manufactured by Ajinomoto Fine Techno Co., -710 (uretene oligomer), Polyflow No. 50E, No. 300 (acrylic copolymer) "manufactured by Kusumoto Chemical Industry Co., &Quot; DERMARON KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA- N (naphthalene sulfonic acid-formaldehyde polycondensate), MS, C, SN-B (aromatic sulfonic acid-formaldehyde polycondensate) "," Homogenol L-18 (polymeric polycarboxylic acid) ", EMULGEN 920, 930, 935, 985 (Polyoxyethylene nonylphenyl ether), acetamin 86 (stearylamine acetate) "manufactured by Nippon Lubricant Co., Ltd.," Solspers 5000 (phthalocyanine derivative) ", 22000 (azo pigment derivative), 13240 (Graft polymer), " NIKOL T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemical Co., Ltd., and "Quot; MYS-IEX (polyoxyethylene monostearate) " manufactured by Shin-Etsu Chemical Industry Co., Ltd., " Hinoact T-8000E etc. " manufactured by Kawaken Fine Chemicals Co., Ltd., " Organosiloxane polymer KP341 " Note) "W0 01: a cationic surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan fatty acid esters, , EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", Disperse 6, Disperse 8, Disperse 15, F98, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103 and P103 of Adeka Co., F108, L121, P-123 "manufactured by Sanyo Chemical Industries, Ltd. and" Ionet (trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd.

The resin may be used alone, or two or more resins may be used in combination. In addition, the resin can be obtained by mixing an alkali-soluble resin to be described later with an end-modified polymer having an anchor site to the pigment surface, a graft polymer having an anchor site to the pigment surface, and a block polymer having an anchor site to the pigment surface Or may be used in combination.

Examples of the alkali-soluble resin include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain, May be a resin obtained by modifying an acid anhydride in the polymer. Particularly, a (meth) acrylic acid copolymer is preferable. The N-substituted maleimide monomer copolymer described in JP-A No. 10-300922, the ether dimer copolymer disclosed in JP-A No. 2004-300204, the polymerizable group described in JP-A No. 7-319161 Is also preferable.

In the case of containing the dispersion resin in the coloring composition, the content of the dispersion resin is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is more preferably 5 parts by mass or more, for example, and 10 parts by mass or more is more preferable. The upper limit is more preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.

<<< Alkali-soluble resin >>>

The coloring composition of the present invention may contain an alkali-soluble resin as a resin. By containing an alkali-soluble resin, developability and pattern formation property are improved. The alkali-soluble resin may also be used as the above-mentioned dispersion resin.

The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5000 to 100,000. The number average molecular weight (Mn) is preferably 1,000 to 20,000.

The alkali-soluble resin may be a linear organic polymer or may be appropriately selected from among alkali-soluble resins having at least one group capable of promoting alkali solubility in a molecule (preferably, acrylic copolymer, styrene-based copolymer as a main chain) have.

The alkali-soluble resin will be described.

The alkali-soluble resin is preferably a polyhydroxystyrene-based resin, a polysiloxane-based resin, an acrylic resin, an acrylamide-based resin or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance, , An acrylamide resin, and an acrylic / acrylamide copolymer resin.

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, and a phenolic hydroxyl group. Examples thereof include those soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution , And (meth) acrylic acid is particularly preferable. These acid groups may be only one kind, or two or more kinds.

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

As the 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, a partially esterified maleic acid copolymer, Soluble resin such as an alkali-soluble phenol resin such as a phenol resin, an acidic cellulose derivative having a carboxyl group in the side chain, and an acid anhydride added to a 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.

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. Examples of the polymerizable group include (meth) allyl group and (meth) acryloyl group. The alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin containing a polymerizable group in a side chain.

The alkali-soluble resin containing a polymerizable group may be prepared by reacting an isocyanate group and a hydroxyl group in advance to prepare a compound (a) containing a polymerizable group such as a (meth) acryloyl group and leaving one unreacted isocyanate group And an urethane-modified alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group; An alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond in the molecule; Acid pendant epoxy acrylate resins; An alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a dibasic acid anhydride having a polymerizable double bond; An alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a compound having an isocyanate and a polymerizable group; A resin obtained by subjecting a resin having an ester group on the side chain to a? -Position or an? -Olefin atom or a sulfonate group on? On the? Side described in JP-A-2002-229207 and JP-A-2003-335814 by a basic treatment Alkali-soluble resins; .

Examples of the alkali-soluble resin containing a polymerizable group include a dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (a polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), Viscot R- (All manufactured by Osaka Yuki Kagaku Kogyo Kabushiki Kaisha), Cyclomer P series, Plexel CF200 series (all manufactured by Daicel Chemical Industries Ltd.), Ebecryl 3800 (manufactured by Dai-ichi Yushi Kabushiki Kaisha) -F8 (manufactured by Nippon Shokubai Co., Ltd.) and the like.

The alkali-soluble resin is preferably a copolymer of benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2- hydroxyethyl / (Meth) acrylic acid / other monomers can be preferably used. Also, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate and a copolymer of 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / 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 / methacrylic acid copolymer can also be preferably used.

The alkali-soluble resin is obtained by polymerizing a monomer component comprising a compound represented by the following formula (ED) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as " It is also preferable to include the polymer (a).

(53)

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)

(54)

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

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, or a substituent of a primary or secondary carbon which is difficult to be desorbed by heat, is 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 structural unit derived from a compound represented by the following formula (X).

(55)

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

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

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

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

When the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably from 1 to 15 mass%, more preferably from 2 to 12 mass%, still more preferably from 3 to 10 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 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.

<< Pigment Derivatives >>

The coloring composition of the present invention may contain a pigment derivative.

The pigment derivative is a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a phthalimidomethyl group or the like. As the pigment derivative, it is preferable to contain a pigment derivative having an acidic group or a basic group from the viewpoints of dispersibility and dispersion stability.

Examples of the pigment for constituting the pigment derivative include pyrrolopyrrole pigment, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perine pigment, perylene pigment , Thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, metal complex pigments, and the like.

The acidic group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group or a quaternary ammonium salt thereof, more preferably a carboxylic acid group or a sulfonic acid group, and particularly preferably a sulfonic acid group. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

The content of the pigment derivative is preferably from 1 to 50% by mass, more preferably from 3 to 30% by mass, based on the total mass of the pigment. The pigment derivative may contain only one kind or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

<< Photopolymerization initiator >>

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

The photopolymerization initiator is not particularly limited as long as it has the ability to 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 photosensitized 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 molar 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.

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, and therefore 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, stepper exposure is used for curing exposure. This exposure apparatus may be damaged by the halogen, and it is also necessary to suppress the addition amount of the photopolymerization initiator 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, reference may 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 described in JP-A-10-291969 and the acylphosphine-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds 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 IRGACURE-819 and DAROCUR-TPO (all trade names, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound.

As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of oxime compounds that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

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. have.

IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are suitably used in commercial products. ADEKA ACKNES NCI-831 and ADEKA ACKLS NCI-930 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) Can also be used.

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

Preferably, for example, refer to paragraphs 0274 to 0275 of Japanese Laid-Open Patent Publication No. 2013-29760, the content of which is 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).

(56)

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

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

Examples of the monovalent 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 of the compound represented by formula (OX-1) are shown below, but the present invention is not limited thereto.

(57)

The oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably 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.

The molar extinction coefficient of the compound can be measured by a known method. For example, the measurement is preferably carried out at a concentration of 0.01 g / L using an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent .

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. Within this range, more excellent sensitivity and pattern formability can be obtained.

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

<< Other Ingredients >>

The coloring composition of the present invention may further contain other components such as a solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, and an organic carboxylic acid anhydride in addition to the components described above, do.

<<< Organic solvents >>>

The coloring composition of the present invention may contain a solvent.

The solvent is not particularly limited so long as it satisfies the solubility of each component and the coating property of the coloring composition, but is preferably selected in consideration of the solubility, coatability, and safety of the colorant oligomer (A) and the polymerizable compound .

As the solvent,

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl lactate, Ethyl lactate, alkyloxyacetate (for example, methyl oxycetate, ethyl oxyacetate, butyl oxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetic acid Ethyl), 3-oxypropionic acid alkyl esters (for example, methyl 3-oxypropionate, ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxyphosphate Ethyl propionate, propyl 2-oxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate,

As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene Glycol ethylacetate, propylene glycol propyl ether acetate and the like,

Examples of the ketones include methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, etc., and

As the aromatic hydrocarbon, for example, toluene, xylene and the like are suitably used.

From the viewpoints of solubility of the dye-sensitized compound (A), the polymerizable compound, etc., and the shape of the coated surface, it is also preferable to mix two or more of these solvents. Examples of the solvent include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, A mixed solution composed of at least two members selected from onium, cyclopentanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable Do.

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

The coloring composition of the present invention 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.

<<< Crosslinking agent >>>

The coloring composition of the present invention may contain a crosslinking agent. 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. For example, a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group and an acyloxymethyl group, (c) phenol compounds, naphthol compounds or hydroxyanthracene compounds substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. Among them, a polyfunctional epoxy resin is preferable.

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

When the coloring composition of the present invention contains a crosslinking agent, 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%, based on the total solid content of the coloring 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.

<<< polymerization inhibitor >>>

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

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- -t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxylamine cerium salt.

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.

For example, by containing the fluorine-containing surfactant, the liquid property (particularly, fluidity) when prepared as a coating liquid is further improved. That is, when a film is formed using a coloring composition containing a fluorine-containing surfactant, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, and coating property to the surface to be coated is improved . Therefore, 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 suitably 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-storing property, 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, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, (Manufactured by Asahi Glass Co., Ltd.), SC-103, SC-104, SC-105, SC-1068, SC-381, PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

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

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

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

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

When the surfactant is contained in the coloring composition of the present invention, the content of the surfactant 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 composition of the present invention may contain only one kind of surfactant or two or more kinds of surfactants. 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, and / or an organic carboxylic acid anhydride. The molecular weight of the organic carboxylic acid and the organic carboxylic acid anhydride is preferably 1000 or less. 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 and / or an organic carboxylic acid anhydride, the content of the organic carboxylic acid and / or organic carboxylic acid anhydride is preferably 0.01 to 10% by mass, More preferably 5 to 5% by mass, and still more preferably 0.05 to 3% by mass.

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 the coloring composition of the present invention, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be incorporated, 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.

In the preparation of 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. The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), 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, and 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 the subsequent step.

When using a filter, different 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. The pore diameter here can refer to the nominal value of the filter manufacturer. Examples of commercially available filters include various filters provided by Nippon Oil Corporation, Advantech Toyobo Co., Ltd., Nippon Integrity Corporation (formerly Nippon Mics Co., Ltd.) or Kitsch Microfilter, Filter.

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 forming coloring patterns of solid-state image pickup devices such as a charge coupled device (CCD), complementary metal oxide semiconductor (CMOS), and color filters used in image display devices such as liquid crystal display devices Can be suitably used. 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.

<Color Filter, Pattern Forming Method, and Color Filter Manufacturing Method>

Next, the color filter, the pattern forming method and the color filter of the present invention will be described in detail with reference to their manufacturing methods. A method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

The color filter of the present invention is formed using the coloring composition of the present invention.

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

The pattern forming method of the present invention can be suitably applied to the formation of a coloring pattern of a color filter.

In the pattern forming method of the present invention, the pattern formation may be performed by the so-called photolithography method, or the pattern formation may be performed by the dry etching method.

That is, the first aspect of the method for producing a color filter of the present invention is characterized in that the step of forming the coloring composition layer by applying the coloring composition of the present invention on a support, the step of exposing the coloring composition layer in a pattern form, To form a colored pattern. If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed colored pattern (post-baking step) may be provided.

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

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 the support, a substrate for a solid-state imaging element provided with a solid-state 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 solid-state imaging element formation surface side (surface) of the substrate for a solid-state imaging element, or on the solid-state imaging element formation surface side (back surface).

On the support, if necessary, an undercoat layer may be provided for improving adhesion with the upper layer, preventing diffusion of the substance, or planarizing the surface of the substrate.

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

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

<< When Pattern is Formated by Photolithography (First Embodiment) >>

<<< Exposure Process >>>

Next, the colored composition layer formed on the support is exposed in a pattern (exposure step). For example, pattern exposure can be performed by exposing a colored composition layer formed on a support through a mask having a predetermined mask pattern by using an exposure apparatus such as a stepper. Thereby, the exposed portion can be cured.

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) of, for example 30 ~ 1500mJ / cm ² are preferred, and 50 ~ 1000mJ / cm ² is more preferably, 80 ~ 500mJ / cm ² is most preferred.

The film thickness of the cured film is preferably 1.0 占 퐉 or less, more preferably 0.1 to 0.9 占 퐉, and still more preferably 0.2 to 0.8 占 퐉. When the film thickness is 1.0 占 퐉 or less, high resolution and high adhesion are likely to be obtained.

<<< Pattern formation process >>>

Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming step). The development of the unexposed portion can be removed by using a developing solution. As a result, the colored composition layer in the unexposed portion in the exposure process is eluted into the developer, leaving only the photo-cured portion.

As the developer, an organic alkali developing solution which does not cause damage to the underlying solid-state image sensor or circuit is preferable.

The temperature of the developing solution is preferably 20 to 30 占 폚, for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removing property, the step of removing the developing solution every 60 seconds and further 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, 1,8-diazabicyclo- [5,4,0] -7-undecene and the like. An alkaline aqueous solution diluted with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, of these alkaline agents is preferably used as the developer.

An inorganic alkali may be used for the developer. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, 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.

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

Post baking is a post-development heat treatment for making the curing to be complete, and the heating temperature is preferably, for example, 100 to 240 占 폚, more preferably 200 to 240 占 폚.

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.

<< In the Case of Pattern Formation by Dry Etching (Second Embodiment) >>

The pattern formation by the dry etching method can be carried out by forming a colored layer by curing the colored composition layer formed on the support and then by using the etching gas using the patterned photoresist layer as a mask .

Specifically, a positive or negative radiation-sensitive composition is coated on the colored layer and dried to form a photoresist layer. In forming the photoresist layer, it is preferable to further perform the pre-baking treatment. Particularly, as the 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 layer, a positive radiation-sensitive composition sensitive to radiation such as deep ultraviolet rays including an ultraviolet ray (g line, h line, i line), an excimer laser, electron beam, ion beam and X ray is preferable . Among the radiation, g line, h line and i line are preferable, and i line is more preferable.

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

The thickness of the photoresist layer is preferably 0.1 to 3 占 퐉, more preferably 0.2 to 2.5 占 퐉, and still more preferably 0.3 to 2 占 퐉. The method of applying the positive-type radiation-sensitive composition can be suitably carried out by using the coating method in the above-described coloring layer.

Then, 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 can be performed by suitably optimizing the conventionally known technique of the photolithography without particular limitation. A resist pattern serving as an etching mask used in the next etching is provided on the colored layer by providing a group of resist through holes 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 coloring pattern is to be formed by developing with a developer.

Any developer that can dissolve the unexposed portions of the positive resist and the negative resist without affecting the colored layer can be used. For example, a combination of various solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving 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. In the case of using an alkaline aqueous 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. It is preferable that the group of through holes is provided on the coloring layer, for example, 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 performed in the following manner, from the viewpoint of forming the cross-section of the pattern closer to a rectangle or further reducing the damage to the support.

Fluorine-based gas and the oxygen gas (O ₂₎ after the first step etching and the etching the first step for performing etching using a mixed gas to the region (D) are not the support is exposed to the nitrogen gas (N ₂₎ and oxygen gas It is preferable to use a mixed gas of oxygen (O ₂ ), preferably a second-stage etching process for performing etching up to a region (depth) where the substrate is exposed, and an over-etching process performed after the substrate is exposed. Hereinafter, a specific method of dry etching, first-stage etching, second-stage etching, and over-etching will be described.

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

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

(2) The time for etching the desired thickness in the first-stage etching and the time for etching the desired thickness in the second-stage etching are respectively calculated.

(3) The first-stage etching is performed according to the etching time calculated in the above-mentioned (2).

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

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

As the mixed gas used in the first-stage etching process, it is preferable that the mixed gas includes fluorine-based gas and oxygen gas (O ₂ ) from the viewpoint of processing the organic material as the etching film into a rectangular shape. In addition, the first-stage etching step may be performed so as to etch to a region where the support is not exposed, so that damage to the support can be avoided. In the second etching step and the overetching step, etching is performed to a region where the support is not exposed by the mixed gas of the fluorine gas and the oxygen gas in the first etching step, and then, from the viewpoint of damage avoidance of the support, It is preferable to perform the etching treatment using a gas mixture of gas and oxygen gas.

It is important that the ratio of the etching amount in the first step etching step to the etching amount in the second step etching step is determined so as not to inhibit the rectangularity by the etching treatment in the first step etching step. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching step and the etching amount in the second-step etching step) is preferably in a range of greater than 0% and less than 50% 20% is more preferable. 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 stucking the peeling liquid or the solvent is not particularly limited, but is preferably several tens of 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 noncyclic nitrogen compound is preferably a noncyclic 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. Of these, 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 more preferably at least one member selected from N-methyl-2-pyrrolidone and N-ethylmorpholine as the cyclic nitrogen compound, and the 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 the peeling liquid, it is preferable that the content of the non-cyclic nitrogen compound is 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the peeling liquid, and the content of the cyclic nitrogen compound is 65 parts by mass or more to 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, as the other process, if necessary. 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 and 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. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the color filter of 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 .

It is also possible to use a configuration having a condensing means (for example, a microlens or the like hereinafter) on the device protective layer and below the color filter (near the support) or a configuration having a condensing means on the color filter .

<Image Display Device>

The color filter of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. And is particularly suitable for use in a liquid crystal display device. The liquid crystal display device provided with the color filter of the present invention is capable of displaying a high-quality image with good display tones and excellent display characteristics.

For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, " Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the " next generation liquid crystal display technology ".

The color filter of the present invention may be used in a color TFT (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 Kyoritsu Shootpan Co., Ltd., 1996) ". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

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 usual required characteristics as described above. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA-type liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

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

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "Market for Liquid Crystal Display Materials and Chemicals," issued by Shimadzu Corporation (1994), "2003," Current Status and Future Prospects of Liquid Crystal Related Markets Published by Fuji Chimera Soken Co., Ltd., 2003).

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

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and a red, green, and blue light emitting diode (LED) 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 more concretely with reference to Examples, but the present invention is not limited to the following Examples unless it is beyond the scope of the present invention. Unless otherwise stated, "% " and " part " are based on mass.

&Lt; Synthesis of xanthene compound (A-xt-1) >

(58)

&Lt; Synthesis of intermediate 1 &gt;

31 parts of 3,6-dichlorosulfofluorane (DCSF) (Zukai Kasei), 67 parts of 2,6-diisopropylaniline, 17 parts of zinc chloride and 120 parts of sulfolane were placed in a flask, Lt; / RTI &gt; 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, 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 intermediate 1 and 50 parts of phosphorus oxychloride were placed in a flask and stirred at 60 占 폚 for 4 hours. The mixture was cooled to room temperature, the reaction solution was added dropwise to 150 parts of ice water, and the mixture was stirred for 30 minutes. The obtained crystals were separated by filtration and washed with 20 parts of water. Thereafter, the obtained crystals were dissolved in 150 parts of chloroform and subjected to Celite filtration. The filtrate was washed with 100 parts of 5% saline solution and 100 parts of 15% saline solution. The filtrate was dried over sodium sulfate, and then 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% aqueous ammonia was added dropwise to maintain 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 obtained 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 was added dropwise thereto so that the temperature of the reaction solution did not exceed 30 占 폚. The reaction solution was stirred at room temperature for 1 hour, concentrated under reduced pressure, and then 90 parts of ethyl acetate, 80 parts of saturated brine, and 10 parts of saturated aqueous sodium bicarbonate were added thereto, and liquid separation operations were carried out. 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 blow-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, Neostan U-600 Nittogase Co., Ltd.) was added, and the mixture was stirred at 85 占 폚 for 1 hour. Subsequently, 500 parts of ethyl acetate and 500 parts of saturated saline solution were added to the solution, and liquid separation operation was carried out. 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.

&Lt; Synthesis of xanthine compound (A-xt-1) &gt;

5 parts of intermediate 5, 50 parts of methylene chloride and 3.4 parts of triethylamine 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-1.

(A-xt-2), (A-xt-4), (A-xt-6) , (A-xt-15)

(A-xt-2), (A-xt-4), (A-xt-6), (A-xt-15) was synthesized in the same manner as the xanthene compound (A-xt-1).

&Lt; Synthesis of dye multimer represented by general formula (1) >

[Synthesis of pigment multimer S-1]

[Chemical Formula 59]

, 1.0 part of a polyfunctional thiol (a compound having the structure of the above (SH-1), manufactured by SC Yuki Kagaku Kogyo Co., Ltd.), 13.7 parts of a xanthene compound (A-xt-1), 2.1 parts of methacrylic acid (MAA) And 9.0 parts of cyclohexanone was heated to 80 占 폚 under a nitrogen stream. To this was added 2,2'-azobis (isobutyrate) dimethyl [V-601; Manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 80 占 폚 for 2 hours. Further, 0.254 parts of V-601 was added, and the mixture was heated and stirred at 80 DEG C for 2 hours, and further heated and stirred at 90 DEG C for 2 hours. After cooling to room temperature, 30.7 parts of cyclohexanone, 0.32 parts of tetrabutylammonium bromide (TBAB) and 1.8 parts of glycidyl methacrylate (GMA) were added and the mixture was heated and stirred at 80 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, followed by re-precipitation to obtain a colorant oligomer S-1.

The weight average molecular weight (in terms of polystyrene) of the pigment oligomer S-1 was 14500, and the acid value was 40 mgKOH / g by titration using a 0.1 N aqueous sodium hydroxide solution.

The number of repeating units having a dye structure of the polymer chain Q in NMR (nuclear magnetic resonance) measurement was calculated as 4.5 on average. Further, a solution containing 0.01 mg / ml of the colorant oligomer S-1 dissolved in tetrahydrofuran (THF) (concentration adjusted to a maximum absorbance of 1.0) was prepared, and the absorbance of this solution at 25 캜 was measured, The maximum absorption wavelength (? Max) was 535 nm and the specific absorption of the maximum absorption wavelength (? Max) was 44 as measured using a cell having an optical path length of 1 cm.

[Synthesis of pigment multimer S-2 to 52]

Was prepared in the same manner as in the synthesis of the colorant oligomer S-1, except that the amount and type of the polyfunctional thiol, various monomers, the amount of V-601, the amount of GMA, and the amount of TBAB were changed to the following table, -2 to S-52.

&Lt; Measurement of specific absorbance &

Each of the colorant oligomers 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 , And the following 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 multimer in the solution in units of mg / ml.

[Table 1]

The types of monomers listed in the table are shown below.

(60)

(61)

(62)

(63)

Comparative Samples (S'-1), (S'-2), (S'-3)

&Lt; EMI ID =

(Synthesis of comparative dye (S'-3)

(65)

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

15 g of triarylmethane compound (A-tp-101), 10 g of hydroxyethyl methacrylate, 5.5 g of methacrylic acid and 5 g of azobisisobutyronitrile were added to a solution of N- ethyl Pyrrolidone (70 g), and the mixture was stirred at room temperature for 30 minutes and dissolved (dropping polymerization solution).

Separately, 15 g of triarylmethane compound (A-tp-101), 10 g of hydroxyethyl methacrylate and 5.5 g of methacrylic acid were dissolved in a vessel and stirred at 80 ° C. The prepared polymerization solution for dropwise addition was added dropwise over 3 hours, and after stirring for 1 hour, azoisobutyronitrile (2.5 g) was added and the reaction was further terminated for 2 hours. After cooling to room temperature, the solvent was distilled off to obtain a comparative dye 3. The weight average molecular weight (Mw) of the comparative dye 3 was 18000, and the acid value was 1.81 mgKOH / g by titration using a 0.1 N aqueous sodium hydroxide solution.

&Lt; Example 1 >

1. Preparation of resist solution

The components of the following composition were mixed and dissolved, followed by filtration with a 0.45 μm nylon filter to prepare a resist solution for the undercoat layer.

Composition of resist solution for undercoat layer

Solvent: propylene glycol monomethyl ether acetate Section 19.20

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

Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 12.20 part

Polymerization inhibitor: p-methoxyphenol 0.0061 part

· Fluorochemical surfactant: F-475, manufactured by DIC Co., Ltd. 0.83 part

Photopolymerization initiator: A trihalomethyltriazine-based photopolymerization initiator (TAZ-107, manufactured by Midori Kagaku Co., Ltd.) 0.586 part

2. Fabrication of silicon wafer substrate with undercoat layer

A 6 inch silicon wafer was heat treated 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 (Preparation of Pigment Dispersion P1 (C.I. Pigment Blue 15: 6 Dispersion)

A pigment dispersion P1 (C.I. Pigment Blue 15: 6 dispersion) was prepared in the following manner.

19.4 parts by mass (average primary particle size: 55 nm) of CI Pigment Blue 15: 6 (hereinafter, also referred to as "PB 15: 6") and 2.95 parts by mass of dispersion resin BY- 2.95 parts by mass (9.93 parts by mass of the solution) of an alkali-soluble resin J1 (copolymer of methacrylic acid benzyl / methacrylic acid, 30% PGMEA solution) and 165.3 parts by mass of PGMEA were mixed with beads mill) (zirconia beads 0.3 mm in diameter) for 3 hours. Thereafter, dispersion treatment was further carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by NIPPON BIO INC.) Equipped with a pressure reducing mechanism. This dispersion treatment was repeated 10 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.

Alkali-soluble resin J1

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3-2. Preparation of coloring composition

The following components were mixed, dispersed and dissolved, and filtered through a 0.45 mu m nylon filter to obtain a colored composition.

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 (ARCICURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.23 parts

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

· Cyclohexanone solution of the colorant multimer (solid content concentration 12.3%): 24.57 parts

Pigment dispersion P1 (C.I. Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 51.40 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 (F475, 1% PGMEA solution, manufactured by DIC): 2.50 parts

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, an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was used to expose the pattern at an exposure dose of 50 to 1200 mJ / cm ² through an Island pattern mask having a wavelength of 365 nm and a square of 1.0 μm.

Thereafter, the silicon wafer substrate on which the irradiated coated film was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by KEMITRONICS Co., Ltd.), and CD-2000 (manufactured by FUJIFILM ELECTRONIC MATERIALS Ltd.) for 60 seconds at 23 ° C to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.

The silicon wafer on which the colored pattern was formed was fixed to a horizontal rotary table by a vacuum chucking method and pure water was supplied from the spray nozzle in a shower shape while rotating the silicon wafer at a rotation speed of 50 rpm by a rotary device, Treatment. Thereafter, spray drying was performed and post baking was performed on 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 a coloring pattern having an exposure amount of 1.0 mu m in pattern size.

<< Evaluation of Development Residues >>

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: Residues were not observed at all outside the coloring pattern forming area (unexposed area).

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

C: 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: Residues were remarkably confirmed outside the coloring pattern forming area (unexposed area).

<< Evaluation of Dyeability >>

The absorbance of the colored pattern in each color filter was measured by MCPD-3000 (manufactured by Otsuka Denshi Co., Ltd.) (absorptivity A).

A CT-2000L solution (manufactured by FUJIFILM ELECTRONICS, INC., Made by Clearfactory Co., Ltd.) was applied on the colored pattern formation side of the color filter so as to have a dry film thickness of 1 mu m and dried to form a transparent film, For 5 minutes.

After completion of the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with MCPD-3000 (manufactured by Otsuka Denshi Co., Ltd.) (absorbance B).

The ratio [%] of the absorbance A to the value of the absorbance A of the coloring pattern measured before heating was calculated with respect to the absorbance B of the obtained transparent film (the following formula (A)). This was used as an index for evaluating the migration to adjacent pixels.

(Formula A) diatom (%) = (absorbance B / absorbance A) x 100

A: less than 1%

B: 1% or more and less than 3%

C: 3% to less than 10%

D: 10% or more

<< Light fastness evaluation >>

The thus-prepared colored photosensitive composition was applied to a glass substrate using a spin coater (manufactured by MICA INC.) To form a coated 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 color filter layer were formed using a light resistance tester (SX- , And a humidity of 50% for 10 hours.

The color difference (? E * ab) before and after the light resistance test was measured by a spectrophotometer MCPD-3000 (manufactured by Otsuka Denshi 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:? E * ab is 3 or less

B:? E * ab is larger than 3 and not larger than 5

C:? E * ab is greater than 5 and less than 10

D:? E * ab is greater than 10

<< Evaluation of flatness >>

1.0 mL of the coloring composition prepared above was applied to a 4-inch silicon wafer using a spin coater (manufactured by MICA INC.) To form a coating film. Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 占 폚 so that the dry film thickness of the center portion of this coating film was 0.60 占 퐉 to form a colored layer.

The film thickness of the colored layer was measured using an optical film thickness meter (Film Matrix Co., Ltd. F20). The smaller the difference between the thinnest portion (central portion) and the thickest portion (peripheral portion), the better. 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: The difference in film thickness is 0.02 占 퐉 or less

B: The difference in film thickness is larger than 0.02 μm and smaller than or equal to 0.05 μm

C: The difference in film thickness is larger than 0.05 占 퐉.

&Lt; Examples 2 to 52 and Comparative Examples 1 to 3 >

Except that the pigment dispersion, the pigment oligomer (dye), the photopolymerization initiator, the alkali-soluble resin and the polymerizable compound 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, and the development residue, flame retardancy, light resistance and flatness were evaluated in the same manner as in Example 1.

In Comparative Examples 1 to 3, the above-described comparative colorants S'-1 to S'-3 were used as colorant oligomers.

[Table 2]

From the above results, the coloring compositions of Examples 1 to 52 were excellent in flame retardancy, light resistance, and flatness. Further, the development residue was very small and the developability was excellent.

On the other hand, in Comparative Examples 1 to 3, either of the flame retardancy or the flatness was poor.

&Lt; Examples 53 and 54 >

The following components were mixed, dispersed and dissolved, and filtered through a 0.45 mu m nylon filter to obtain a colored composition.

Next, the obtained color composition was coated on a glass substrate of 7.5 cm x 7.5 cm using a spin coater so that the film thickness became 0.5 m, and heated at 200 캜 for 5 minutes using a hot plate, The film was cured to prepare a colored 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.

Subsequently, 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), and the photoresist layer was exposed at a temperature of 90 ° C for 1 minute, Heat treatment was carried out. Thereafter, development processing was performed for one minute with a developing solution " FHD-5 " (manufactured by FUJIFILM ELECTRONIC MATERIALS), and post baking treatment was further performed 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 glass substrate on which the photoresist layer was formed was attached to an 8-inch silicon wafer, and the wafer was irradiated with an RF power of 800 W, an antenna bias of 400 W, a wafer bias of 200 W, the internal pressure of the chamber: 4.0Pa, substrate temperature: 50 ℃, the gas species and flow rates of mixed gases CF _4: 80mL / min., O _2: 40mL / min, Ar:. to a 800mL / min, 80 seconds of the first step Etching treatment was performed.

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.

After performing the dry etching under the above conditions, the resist was removed using a photoresist stripping liquid "MS230C" (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD.) At 50 ° C for 120 seconds to remove the resist to form a 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.

The obtained color filter was evaluated for flame resistance, light resistance and flatness in the same manner as in Example 1. [

&Lt; Composition of coloring composition >

Organic solvent (cyclohexanone): 17.12 parts

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

· Cyclohexanone solution of the colorant multimer (solid content concentration 12.3%): 24.57 parts

Pigment dispersion (see table below): 51.40 parts

Polymerization inhibitor (p-methoxyphenol): 0.0007 part

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

[Table 3]

From the above results, the coloring compositions of Examples 53 and 54 were excellent in flame retardancy, light resistance, and flatness.

The abbreviations of the compounds listed in the Tables are as follows.

Photopolymerization initiator:

(67)

Alkali-soluble resin: The following structure

(68)

Polymerizable compound

Z-1: Ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin Nakamura Kagaku)

Z-2: dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Z-3: Ethoxylated (4) pentaerythritol tetraacrylate, SR494 (manufactured by Satomar)

Z-4: ethoxylated (3) trimethylol propyl acrylate, SR454 (manufactured by Satoromer)

Z-5: ethoxylated (6) trimethylolpropane acrylate, SR499 (manufactured by Satoromer)

Z-6: KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co.)

Z-7: tris (2-hydroxyethyl) isocyanurate triacrylate, SR368 (manufactured by Satoromer)

Pigment dispersion

Pigment dispersion P2 (C.I. Pigment Blue 15: 6 dispersion):

A pigment dispersion P2 was prepared in the same manner as in the preparation of the pigment dispersion P1 except that the following dispersion resin D1 was used instead of the dispersion resin BY-161.

(69)

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

Pigment dispersion P3 (C.I. Pigment Blue 15: 6 dispersion):

A pigment dispersion P3 was prepared in the same manner as in the preparation of the pigment dispersion P1 except that the following dispersion resin D2 was used instead of the dispersion resin BY-161.

(70)

Mw = 20000, x / y = 15/85 (mass ratio), n = 20, acid value = 100 mgKOH / g

Pigment dispersion P4 (C.I. Pigment Violet 23 dispersion):

A pigment dispersion P4 was prepared in the same manner as the preparation of the pigment dispersion P1 except that C. I. Pigment Violet 23 was used instead of PB 15: 6 as the pigment in the preparation of the pigment dispersion P1.

Pigment dispersion P5 (C.I. Pigment Red 254 dispersion):

A pigment dispersion P5 was prepared in the same manner as the preparation of the pigment dispersion P1 except that C.I. Pigment Red 254 was used instead of PB 15: 6 as the pigment in the preparation of the pigment dispersion P1.

Pigment dispersion P6 (C.I. Pigment Green 58 dispersion):

A pigment dispersion P6 was prepared in the same manner as the preparation of the pigment dispersion P1 except that C. I. Pigment Green 58 was used instead of PB 15: 6 as the pigment in the preparation of the pigment dispersion P1.

Pigment dispersion P7 (C.I. Pigment Yellow 139 dispersion):

A pigment dispersion P7 was prepared in the same manner as in the preparation of the pigment dispersion P1 except that C.I. Pigment Yellow 139 was used instead of PB 15: 6 as the pigment in the preparation of the pigment dispersion P1.

Claims (18)

A coloring composition comprising a pigment multimer represented by the general formula (2) and a polymerizable compound;

In the general formula (2), A ¹ represents an n-valent linking group, a group consisting of one or more kinds selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in its main chain,
B ¹ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR-, R represents a hydrogen atom, An alkyl group or an aryl group,
C ¹ represents a single bond, an alkylene group, an arylene group, or an oxyalkylene group,
S represents a sulfur atom,
Q represents a polymer chain having a repeating unit represented by the general formula (a1-1), wherein the average value of the number of repeating units represented by the general formula (a1-1) of n Q is 2 or more,
n represents an integer of 3 to 10,

In the general formula (a1-1), Q ¹ represents a trivalent linking group formed by polymerization,
L ¹ represents a single bond or an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic group, -CH═CH-, -O-, -S-, -C (═O) _{2 -, -NR-, -CONR-, -O} 2 C-, -SO-, -SO 2 - and them represents a divalent linking group selected from a group formed by connecting 2 or more, R is a hydrogen atom, an alkyl group , An aryl group, or a heteroaryl group,
D ¹ is at least ^{one selected} from the group consisting of triarylmethane dyes, xanthine dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, azo dyes and dipyramethane dyes And a dye structure derived from a dye selected from the group consisting of
"*" Indicates the hand joined with the main chain. A coloring composition comprising a pigment multimer represented by the general formula (1) and a polymerizable compound;
P- (Q) _n ... (One)
In the general formula (1), P represents a linking group derived from a polyhydric thiol as a linking group of n,
Q represents a polymer chain having a repeating unit represented by the general formula (a1-1), wherein the average value of the number of repeating units represented by the general formula (a1-1) of n Q is 2 or more,
n represents an integer of 3 to 10,

In the general formula (a1-1), Q ¹ represents a trivalent linking group formed by polymerization,
L ¹ represents a single bond or an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic group, -CH═CH-, -O-, -S-, -C (═O) _{2 -, -NR-, -CONR-, -O} 2 C-, -SO-, -SO 2 - and them represents a divalent linking group selected from a group formed by connecting 2 or more, R is a hydrogen atom, an alkyl group , An aryl group, or a heteroaryl group,
D ¹ is at least ^{one selected} from the group consisting of triarylmethane dyes, xanthine dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, azo dyes and dipyramethane dyes And a dye structure derived from a dye selected from the group consisting of
"*" Indicates the hand joined with the main chain. The method according to claim 1 or 2,
Wherein said dye multimer has a specific absorption at a maximum absorption wavelength of 400 nm to 800 nm represented by the following formula (A?) 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 pigment multimer in the solution in units of mg / ml. The method according to claim 1 or 2,
Wherein the colorant composition contains 1 to 50 mass% of the colorant multimer relative to the total solid content of the colorant composition. The method according to claim 1 or 2,
The dye multimer can be obtained by reacting a compound represented by the general formula (3) with a compound selected from the group consisting of a triarylmethane dye, a zanthone dye, an anthraquinone dye, a cyanine dye, a squarylium dye, a quinophthalone dye, Wherein the coloring composition is obtained by radical polymerization of a compound having a pigment structure and a radical polymerizable group derived from a pigment selected from phthalocyanine coloring matter, azo coloring matter and dipyramethine coloring matter.
P ⁰ - (SH) _n ... (3)
In the general formula (3), P ⁰ is an alkyl group having 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And an n-linking group consisting of 0 to 20 sulfur atoms, which is a linking group derived from a polyhydric alcohol,
SH represents a thiol group,
n represents an integer of 3 to 10; The method according to claim 1 or 2,
And a colorant other than the colorant multimer. The method according to claim 1 or 2,
And a photopolymerization initiator. The method according to claim 1 or 2,
And Q has at least one kind selected from repeating units having an acid group and repeating units having a polymerizable group. The method according to claim 1 or 2,
Wherein Q is one kind selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin. The method of claim 2,
The connecting group of n in the formula (P) is represented by any one of formulas (P-1) to (P-32).

In the formula (P-32), each n independently represents an integer of 0 or more. A color filter comprising the coloring composition according to claim 1 or 2. A step of applying the coloring composition according to claim 1 or 2 on a support to form a coloring composition layer,
A step of exposing the colored composition layer in a pattern shape,
A step of developing and removing the unexposed portion of the colored composition layer exposed in a pattern shape to form a colored pattern
&Lt; / RTI &gt; A step of applying the coloring composition according to claim 1 or 2 on a support to form a coloring composition layer and curing to form a colored layer,
A step of forming a photoresist layer on the colored layer,
Patterning the photoresist layer by exposure and development to obtain a resist pattern;
A step of dry-etching the colored layer using the resist pattern as an etching mask to form a colored pattern
/ RTI &gt; A manufacturing method of a color filter, comprising the pattern forming method according to claim 12. A method of manufacturing a color filter, comprising the pattern forming method according to claim 13. A solid-state imaging device having the color filter according to claim 11. An image display apparatus having the color filter according to claim 11. A process for producing a pigment multimer comprising radical polymerization of a compound represented by the general formula (4) and a compound having a pigment structure and a radically polymerizable group.
A ⁰ - (B ⁰ -C ⁰ -SH) _n - (4)
In the general formula (4), A ⁰ represents a linking group of n,
B ⁰ represents a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR-,
R represents a hydrogen atom, an alkyl group or an aryl group,
C ⁰ represents a single bond or a divalent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10;