KR20160102286A - Coloring composition, pattern formation method, color filter manufacturing method, color filter, solid-state imaging element, image display device, and method for manufacturing coloring composition - Google Patents

Abstract

A method of producing a color filter, a method of manufacturing a color filter, a color filter, a solid-state image pickup device, an image display, and a method of manufacturing a coloring composition using the coloring composition.
A coloring composition comprising a dye multimer having a dye structure and having a group represented by the following formula at the main chain terminal, and a polymerizable compound; In the general formula (I), Z represents a hydrogen atom or a monovalent substituent; * Represents the bonding position with the main chain terminal; In formula (II), A and B each independently represent a monovalent substituent; A and B may be connected to each other to form a ring; * Represents the bonding position with the main chain terminal.

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring composition, a pattern forming method, a color filter manufacturing method, a color filter, a solid-state image pickup device, an image display device and a manufacturing method of a coloring composition , IMAGE DISPLAY DEVICE, AND METHOD FOR MANUFACTURING COLORING COMPOSITION}

The present invention relates to a coloring composition. The present invention also relates to a pattern forming method, a color filter manufacturing method, a color filter, a solid-state image pickup device, and an image display apparatus. The present invention also relates to a method for producing a coloring composition.

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

The above method has been widely used as a method suitable for the production of a color filter for a color display and the like because it is stable with respect to light or heat in terms of using a pigment and satisfies the positional accuracy in that patterning is performed by photolithography .

On the other hand, in recent years, with the miniaturization and thinning of color filters, solvent resistance, which has not been a problem in the past, becomes a problem.

Here, as the photosensitive resin composition for a color filter, Patent Document 1 and Patent Document 2 are known. Patent Document 1 discloses an alkali-soluble resin prepared with a specific chain transfer agent in order to improve color resist properties. Patent Document 2 discloses that the light resistance is improved by a block copolymer of a dye and a photostabilizer.

Patent Document 1: International Publication No. 2007/029871 Patent Document 2: JP-A-2003-342494

The inventors of the present invention have examined Patent Documents 1 and 2, and found that the light resistance is poor.

An object of the present invention is to provide a colored composition excellent in solvent resistance and light fastness. A color filter, a solid-state image pickup device, and an image display device using the coloring composition. The present invention also relates to a method for producing a coloring composition.

The present inventors have studied in detail and found that the above problems can be solved by using a dye multimer having a specific substituent at the main chain terminal.

Concretely, the above-mentioned problem has been solved by the following means <1>, preferably by <2> to <19>.

<1> A coloring composition comprising a dye multimer having a dye structure and having a group represented by formula (I) or a group represented by formula (II) at the main chain terminal, and a polymerizable compound;

The compound of formula (I)

[Chemical Formula 1]

In the general formula (I), Z represents a hydrogen atom or a monovalent substituent; * Represents the bonding position with the main chain terminal;

In general formula (II)

(2)

In formula (II), A and B each independently represent a monovalent substituent; A and B may be connected to each other to form a ring; * Represents the bonding position with the main chain terminal.

&Lt; 2 > The coloring composition according to < 1 >, further comprising a photopolymerization initiator.

<3> The coloring composition according to <1> or <2>, further comprising a pigment.

<4> The coloring composition according to any one of <1> to <3>, wherein the dispersion degree of the colorant multimer is Mw / Mn of 1.0 to 1.8.

<5> The coloring composition according to any one of <1> to <4>, further comprising an alkali-soluble resin.

&Lt; 6 > The coloring composition according to any one of < 1 > to < 5 >, wherein the polymeric multimer is a random polymer of a polymerizable compound containing a dye and a polymerizable compound of another polymerizable compound.

<7> The dye-sensitized solar cell according to any one of <1> to <6>, wherein the dye multimer is at least one of a dipyramethine dye, a triarylmethane dye, a xanthate dye, an azo dye, a cyanine dye, and a squarylium dye. &Lt; / RTI &gt;

<8> The coloring composition according to any one of <1> to <7>, wherein at least one of the colorant multimer is a styrene resin or a (meth) acrylic resin.

<9> The compound according to <1>, wherein Z in the general formula (I) is selected from an amino group, an alkoxy group and an aryloxy group substituted with -SR ¹ , an aryl group, a heteroaryl group, an alkyl group and / ), Wherein A and B each independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and a coloring composition according to any one of <1> to <8>. Wherein R ¹ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a total of 3 to 30 atoms of a carbon atom and a bicyclic atom Represents a monovalent heterocyclic group, and A and B may be connected to each other to form a ring.

<10> The compound according to <10>, wherein Z in formula (I) is -SR ¹ or an aryl group, or A and B in formula (II) are each independently a secondary or tertiary alkyl group having 1 to 30 carbon atoms , A colored composition according to &lt; 9 &gt;; Provided that A and B may be bonded to each other to form a ring.

&Lt; 11 > The coloring composition according to any one of < 1 > to < 10 >

&Lt; 12 > A process for producing a colored composition, 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; exposing the coloring composition layer in a pattern; And forming a colored pattern.

&Lt; 13 > A method of manufacturing a color filter, comprising the pattern formation method according to < 12 >.

<14> A color filter manufactured by a color filter manufactured by using the coloring composition according to any one of <1> to <11> or a method of manufacturing a color filter according to <13>.

<15> A solid-state imaging device having a color filter according to <14>.

&Lt; 16 > An image display apparatus having a color filter according to < 14 >.

<17> A method for producing a coloring composition, which comprises subjecting a polymerizable compound having a dye structure to living radical polymerization and then blending a polymerizable compound.

In the presence of at least one of the compound represented by the general formula (Ia), the compound represented by the general formula (IIa) and the radical represented by the general formula (IIb), the polymerizable compound having a pigment structure and another polymerizable compound A method for producing a coloring composition according to < 17 >

(Ia)

(3)

In the general formula (Ia), Z is synonymous with the general formula (I). C represents a monovalent organic group;

The compound of formula (IIa)

[Chemical Formula 4]

In the general formula (IIa), Z is synonymous with the general formula (II). D represents a monovalent organic group;

(IIb)

[Chemical Formula 5]

In the general formula (IIb), A and B are synonymous with the general formula (II).

<19> The method for producing a coloring composition according to <17> or <18>, wherein the coloring composition is a coloring composition according to any one of <1> to <11>.

According to the present invention, it becomes possible to provide a colored composition excellent in solvent resistance and light resistance. It is also possible to provide a pattern forming method, a color filter manufacturing method, a color filter, a solid-state image pickup device, and an image display device using the above colored composition. In addition, it becomes possible to provide a method for producing a coloring composition.

Hereinafter, the coloring composition, the pattern forming method, the color filter manufacturing method, the color filter, the solid-state image pickup device and the image display device of the present invention will be described in detail. The production method of the coloring composition will be described.

The following description of constituent elements in the present invention is based on a representative embodiment of the present invention, but the present invention is not limited to such embodiments.

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

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

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

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

In the present specification, the solid content concentration refers to the solid content concentration at 25 占 폚.

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

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

In the present specification, 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.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a colored composition excellent in color characteristics.

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 measured by using, for example, HLC-8220 (manufactured by TOSOH CORPORATION), TSKgel Super AWM- 6.0 mm ID x 15.0 cm) as the eluent was used, using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

In the present specification, the methyl group may be represented by Me, the ethyl group by Et, the propyl group by Pr, and the phenyl group by PH or Ph.

The coloring composition of the present invention (hereinafter sometimes simply referred to as "the composition of the present invention") has a pigment structure and is a group represented by formula (I) or a group represented by formula (II) , And a polymerizable compound.

The compound of formula (I)

[Chemical Formula 6]

In the general formula (I), Z represents a hydrogen atom or a monovalent substituent. * Represents the bonding position with the main chain terminal.

In general formula (II)

(7)

In the general formula (II), A and B each independently represent a monovalent substituent. A and B may be connected to each other to form a ring. * Represents the bonding position with the main chain terminal.

With such a constitution, solvent resistance and light resistance can be imparted. Further, since the pigment multimer used in the present invention is synthesized by, for example, living polymerization, the dispersion degree (Mw / Mn) of the pigment multimer can be reduced. That is, by slightly decreasing the ratio of the high molecular weight component as the pigment multimer, the light resistance can be further improved, and the solvent resistance can be improved by slightly decreasing the proportion of the low molecular weight component. Further, it is possible to further improve the heat resistance, application property and developability.

Further, in order to improve spectroscopy of the color filter, a dye may be applied instead of a pigment. However, since the dye has poor light resistance and heat resistance as compared with the pigment, the color filter to which the dye is applied may have low durability. In the present invention, even when a dye is used as a dye, these effects can be effectively improved.

The coloring composition of the present invention preferably contains a photopolymerization initiator and / or a pigment, and may contain other components such as a crosslinking agent, if necessary.

Hereinafter, the details of the present invention will be described.

<Coloring matter having a dye structure and having a group represented by the general formula (I) or a group represented by the general formula (II) at the main chain terminal>

The coloring composition of the present invention is a colorant composition having a pigment structure and having a group represented by the general formula (I) or a group represented by the general formula (II) at the end of the main chain (hereinafter sometimes simply referred to as " ). &Lt; / RTI &gt; The dye multimer may contain two or more kinds.

A pigment multimer is a multimer having a partial structure derived from a dye usually having a maximum absorption wavelength in the range of 400 nm to 780 nm in its molecular structure. The dye multimer of the present invention more preferably contains a repeating unit containing a dye monomer, more preferably a repeating unit containing a dye monomer and a repeating unit having a polymerizable group, It is more preferable to include a repeating unit and a repeating unit having a polymerizable group and a repeating unit having an acid group. Further, it is preferable that the dye structure of the present invention has cation sites.

The colorant oligomer functions as, for example, a coloring agent in the coloring composition of the present invention.

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

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

Hereinafter, a group represented by the general formula (I) or a group represented by the general formula (II) (hereinafter sometimes referred to as "specific end group") and a partial structure derived from the dye, Will be explained.

<< Specific Short Term >>

The specific end group is represented by the general formula (I) or (II).

The compound of formula (I)

[Chemical Formula 8]

In the general formula (I), Z represents a hydrogen atom or a monovalent substituent. * Represents the bonding position with the main chain terminal;

In the general formula (I), Z represents a monovalent substituent. Z represents a hydrogen atom, a halogen atom, a carboxyl group, a cyano group, an alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a total of 3 to 30 a monovalent heterocyclic ^{group, -OR 1, -SR 1, -OC} (= O) R 1, -N (R 1) (R 2), -C (= O) OR 1, -C (= O) N ( R ¹ ) (R ² ), -P (═O) (OR ¹ ) ₂ , -P (═O) (R ¹ ) ² or a polymer chain is preferred, and -SR ¹ , An aryl group, an amino group substituted with an alkyl group and / or an aryl group, an alkoxy group, and an aryloxy group, and is preferably selected from -SR ¹ (preferably an alkylthio group, an arylthio group) More preferably an alkylthio group or an aryl group, particularly preferably an alkylthio group.

The aryl group as Z is preferably a phenyl group or a naphthyl group. The heteroaryl group as Z is preferably a nitrogen-containing 5-membered ring or a 6-membered ring compound. The amino group substituted with an alkyl group and / or an aryl group as Z is preferably an alkyl group having 1 to 5 carbon atoms or an amino group substituted with a phenyl group. The alkoxy group as Z is preferably an alkoxy group having 2 to 5 carbon atoms. The aryloxy group as Z is preferably a phenoxy group.

R ¹ and R ² each independently represent an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a total of 3 to 30 A monovalent heterocyclic group having 3 to 30 total atoms of a carbon atom and a bivalent atom, R &lt; ^{1 &gt;} and R &lt; ² &^gt; R ² may be all substituted or not substituted. Examples of the substituent when it is substituted include an alkyl group and an aryl group.

R ¹ and R ² are each independently preferably an alkyl group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms or a phenyl group.

In general formula (II)

[Chemical Formula 9]

In the general formula (II), A and B each independently represent a monovalent substituent. A and B may be connected to each other to form a ring. * Represents the bonding position with the main chain terminal.

The monovalent substituents represented by A and B are each independently preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. The alkyl group having 1 to 30 carbon atoms preferably has 3 to 10 carbon atoms.

Particularly, it is preferable that one of A and B is a secondary or tertiary alkyl group having 1 to 30 carbon atoms and the other is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, More preferably one of A and B is an alkyl group having 1 to 30 carbon atoms and one of A and B is a tertiary alkyl group having 1 to 30 carbon atoms and the other is a tertiary alkyl having 1 to 30 carbon atoms, And one of them is particularly preferably a secondary or tertiary alkyl group having 1 to 30 carbon atoms (more preferably a secondary alkyl group having 1 to 30 carbon atoms).

As the substituent which the alkyl group having 1 to 30 carbon atoms may have, an aryl group is preferable, and a phenyl group is more preferable. As the substituent which the aryl group may have, an aryl group is preferable. These groups may be substituted with other substituents. A and B may be bonded to each other to form a ring.

In the present invention, it is particularly preferable that Z in the general formula (I) is -SR ¹ or an aryl group, and A and B in the general formula (II) are each a secondary or tertiary alkyl group having 1 to 30 carbon atoms (Provided that A and B may be bonded to each other to form a ring).

Specific examples of the terminal groups are shown, but the present invention is not limited thereto.

[Chemical formula 10]

(11)

[Chemical Formula 12]

As the method for introducing the polymer main chain, the terminal group represented by the general formula (I) or (II) can be obtained by reacting the compound represented by the general formula (Ia), the compound represented by the general formula (IIa) Radical polymerization of a polymerizable compound having a dye structure in the presence of at least one of radicals is preferred.

(Ia)

[Chemical Formula 13]

In the general formula (Ia), Z is synonymous with the general formula (I). C represents a monovalent organic group.

The compound of formula (IIa)

[Chemical Formula 14]

In the general formula (IIa), Z is synonymous with the general formula (II). D represents a monovalent organic group.

(IIb)

[Chemical Formula 15]

In the general formula (IIb), A and B are synonymous with the general formula (II).

By adding such an additive, inactivation of the terminal activity at the time of radical polymerization becomes an equilibrium state, so that the state of the radicals does not seem to be inactivated. By such polymerization by living radical polymerization, a multimer having a small degree of dispersion can be obtained. In the present invention, it is also preferable that the colorant multimer is a (meth) acrylic resin and / or a styrene-based resin. Here, the (meth) acrylic resin means a resin in which at least 50 mol% of the polymerizable compound as a raw material is (meth) acrylate, and the styrene resin means a resin in which at least 50 mol% Lane resin.

In the present invention, particularly when a compound represented by the general formula (Ia) is used, the (meth) acrylic resin and / or the styrene resin is preferable, and when the compound represented by the general formula (IIa) or the general formula (IIb) (Meth) acrylic resins are preferable.

<< Repeating unit having a pigment structure >>

The repeating unit having the dye structure of the colorant multimer used in the coloring composition of the present invention is not specifically defined, but may be a repeating unit represented by the general formula (A), the general formula (B) shown in paragraphs 0276 to 0304 of JP-A- ) And the structural unit represented by the general formula (C) as a skeleton. 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 include a repeating unit represented by the following general formula (A).

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

<<< Constitutional units represented by the general formula (A) >>>

[Chemical Formula 16]

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

Hereinafter, general formula (A) will be described in detail.

In the general formula (A), X ₁ represents a linking group formed by polymerization. That is, a part forming a repeating unit corresponding to a main chain formed by a polymerization reaction. In addition, the parts indicated by two * are repeated units. X ₁ is preferably a linking group represented by any of the following formulas (XX-1) to (X-24), and is preferably a linking group represented by formulas (XX-1) and Linking chain represented by (XX-10) to (XX-17), (XX-18), (XX-19) and (XX-24) More preferably selected from (XX-1) and (XX-2), a styrene-based connecting chain represented by (XX-10) (Meth) acrylic linkage chain represented by (XX-1) and (XX-2) and a styrene-based linkage chain represented by (XX-11) are more preferable .

(XX-1) to (X-24), it is connected to L ₁ at a site indicated by *. Me represents a methyl group. In the formulas (XX-18) and (XX-19), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

[Chemical Formula 17]

[Chemical Formula 18]

In the general formula (A), L ₁ represents a single bond or a divalent linking group. Examples of the divalent linking group when L ₁ represents a divalent linking group include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc.) , A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group or a naphthalene group), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S-, C (= O) -, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and a linking group formed by connecting two or more thereof. 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, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. An example in which L ₁ includes an anion will be described later.

In the general formula (A), DyeI represents a dye structure derived from a dye compound described later.

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

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

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

<< Color Structure >>

The dye structure used in the present invention is not specifically defined, and a known dye structure can be employed. The dye structure used in the present invention is preferably a dye structure containing a cationic site in the molecule.

Specific examples of the dye include pigments such as a dipyramethine dye, a carbonium dye (diphenylmethane dye, triarylmethane dye, xanthine dye, and acridine dye), an azo dye, a polymethine dye (oxolin dye, A pigment structure derived from a pigment selected from a pigment, an aziridine dye, a styryl dye, a cyanine dye, a squarylium dye, a croconium dye, etc., a subphthalocyanine dye, and a metal complex dye thereof .

Among these dye structures, from the viewpoint of color characteristics, a dye structure derived from a dye selected from a dipyramethine dye, a carbonium dye, and a polymethine dye is preferable, and a dye structure derived from a dipyramethine dye, a triarylmethane dye, The dyestuff structure derived from a dyestuff selected from dyestuffs, dyestuff dyestuffs, dyestuff dyestuffs, dyestuff dyestuffs, dyestuff dyestuffs, dyestuff dyestuff dyestuffs, dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff dyestuff More preferably a dye structure derived from a dye selected from a dipyramethine dye, an azo dye and a xanthine dye, more preferably a dye structure derived from an azo dye and a xanthine dye, desirable. The use of cations having such a pigment structure tends to further improve heat resistance and light resistance.

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).

In the present invention, it is preferable that the dye structure has a cation. Hereinafter, the dye structure preferably used in the present invention will be described in detail.

<<< Dipyromethane coloring >>>

One of the aspects of the dye structure according to the present invention is the structure of the dipyramethine dye shown below.

As the dipyrammethene dye in the present invention, a dipyrammethene compound and a dipyrammethene metal complex compound obtained from a dipyrammethene compound and a metal or a metal compound are preferable. And binds to the polymer at one of these dipyramethine dye structures.

In the present invention, a compound containing a dipyrammethenic structure is referred to as a dipyrammethenic compound, and a complex containing a compound containing a dipyrammethenic structure as a metal or a metal compound is referred to as a dipyrammethenic metal complex compound.

As the dipyrammethene metal complex compound, a dipyrammethene metal complex compound obtained from a dipyrammethene compound represented by the following formula (M) and a metal or a metal compound and a tautomer thereof are preferable, and among them, as a preferred embodiment, (7), or a dipyrammethene metal complex compound represented by the following general formula (8), and the dipyrammethene metal complex compound represented by the general formula (8) is more preferable.

A dipyrammethene metal complex compound obtained from a dipyrammethene compound represented by the formula (M) and a metal or a metal compound, and a tautomer thereof

One of preferred embodiments of the dye structure is a compound in which a compound represented by the following formula (M) (a dipyrammethene compound) or a tribo-isomer thereof is a complex for embedding in a metal or a metal compound (hereinafter appropriately referred to as "specific complex" Containing pigment structure. In the present invention, the following compounds form a cation structure. For example, a metal such as zinc bonded to the nitrogen atom of the formula (M) may form a cation structure.

[Chemical Formula 19]

(In the formula (M), R ⁴ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

The introduction site of the compound represented by the general formula (M) when introduced into the structural units represented by the general formulas (A) to (D) is not particularly limited, and from the viewpoint of the compatibility, R ⁴ to R ⁹ It is preferably introduced at any one site, more preferably introduced in any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ , more preferably introduced in any one of R ⁴ and R ⁹ .

Examples of the monovalent substituent in the case where R ⁴ to R ⁹ in the general formula (M) represent a monovalent substituent include the substituents exemplified in Substituent Group A described later.

When the monovalent substituent represented by R ⁴ to R ⁹ in the general formula (M) is a further substitutable group, it may further have a substituent described for R ⁴ to R ⁹ , or may have two or more substituents , The substituents thereof may be the same or different.

R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ and R ⁸ and R ⁹ in the general formula (M) are each independently bonded to form a 5-membered, 6-membered or 7-membered ring , Or an unsaturated ring may be formed. Provided that R ⁴ and R ⁹ are not bonded to each other to form a ring. When the 5-membered, 6-membered, and 7-membered rings to be formed are further substitutable groups, they may be substituted with the substituents described for R ⁴ to R ⁹ , and when they are substituted with two or more substituents, May be the same or different.

R ⁴ and R ⁵ in the general formula (M), R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ are each independently bonded to form a 5-membered, 6-membered or Examples of the 5-membered, 6-membered or 7-membered ring or unsaturated ring having no substituent in the case of forming a 7-membered ring or an unsaturated ring include pyrrole ring, furan ring, thiophene ring, Pyridine ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexane ring, benzene ring, pyridine ring, pyrazine ring, And preferably a benzene ring or a pyridine ring.

R ¹⁰ in the general formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. The halogen atom, the alkyl group, the aryl group and the heterocyclic group described above are each the same as the halogen atom, the alkyl group, the aryl group and the heterocyclic group of Substituent Group A described below, and the preferred ranges thereof are also the same.

When the alkyl group, aryl group and heterocyclic group in the case where R ¹⁰ represents an alkyl group, an aryl group or a heterocyclic group are further substitutable groups, they may be substituted with the substituents described in the Substituent Group A described later , When they are substituted with two or more substituents, the substituents may be the same or different.

~ Metal or metal compound ~

The specific complex in the present invention is a complex in which a dipyrammethenic compound represented by the general formula (M) or a tautomer thereof represented by the above-mentioned general formula (M) is embedded in a metal or a metal compound.

Here, the metal or metal compound may be any metal or metal compound capable of forming a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. Examples of metals or metal compounds, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, in addition to metals such as Co, Fe, AlCl, InCl, FeCl, TiCl ₂ , Metal chlorides such as SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO ₂ and VO, and metal hydroxides such as Si (OH) ₂ .

Among these, preferred are Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO or VO in view of stability of the complex, spectral characteristics, heat resistance, light resistance, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferable, and Zn is particularly preferable.

Next, a more preferable range of the specific complex of the compound represented by the formula (M) in the present invention will be described.

A preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, , An alkoxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an anilino group, a heterocyclic amino group, a carbonamido group, An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R ⁵ and R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, An alkoxy group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, A sulfonyl group, or a sulfamoyl group; R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, , An acyl group, an alkoxycarbonyl group, a carbamoyl group, an anilino group, a carbonamido group, an ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, , An alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group; R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; The metal or metal compound is in the range of Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO or V =

A more preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, An aryl group, an aryl group, an aryl group, an aryl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, Or a phosphinoylamino group; R ⁵ and R ⁸ are each independently selected from the group consisting of alkyl, alkenyl, aryl, heterocyclic, cyano, nitro, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, A diaryl group, an arylsulfonyl group, or a sulfamoyl group; R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, An alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; Wherein the metal or the metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V =

A particularly preferable range of the specific complex in the present invention is that in the formula (M), R ⁴ and R ⁹ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, An alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R ⁵ and R ⁸ are each independently an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group; R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R ¹⁰ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; The metal or the metal compound is Zn, Cu, Co, or V = O.

The dipyrammethene metal complex compound represented by the general formula (7) or the general formula (8) described below in detail is also a particularly preferable embodiment of the dipyramethine dye.

The dipyrammethene metal complex compound represented by the general formula (7)

One suitable embodiment of the dye structure in a cation having a dye structure is a dye structure derived from a dipyrammethene metal complex compound represented by the following general formula (7). In the present invention, it is preferable that the following compounds form a cation structure. For example, Ma in formula (7) may form a metal cation structure such as zinc.

[Chemical Formula 20]

(In the general formula (7), R ⁴ to R ⁹ each independently represent a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. X ¹ represents a group capable of binding to Ma, X ² represents a group for neutralizing the charge of Ma, X ¹ and X ² are bonded to each other to form a 5 A 6-membered ring, or a 7-membered ring may be formed, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.

The dipyrammethene metal complex compound represented by the general formula (7) includes a tautomer.

The introduction site in the case where the dipyrammethene metal complex compound represented by the general formula (7) is introduced into the structural units represented by the above general formulas (A) to (D) is not particularly limited, ⁴ ~ R preferably introduced in any of the parts of ^{9 and, R 4, R 6, R} 7 and R ^9, and of the more preferred to be introduced in any one, R ⁴ and R ⁹ introduced according to any one of the .

In the case where the dye structure has an alkali-soluble group, as the method of introducing the alkali-soluble group, any one of R ⁴ to R ¹⁰ , X ¹ and X ² in the general formula (7) , An alkali-soluble group can be used. Among these substituents, any one of R ⁴ to R ⁹ and X ¹ is preferable, and any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ is more preferable, and any one of R ⁴ and R ⁹ is more preferable .

The dipyrammethene metal complex compound represented by the general formula (7) may have a functional group other than the alkali-soluble group as long as the effect of the present invention is not impaired.

R ~ ⁴ R ⁹ in the in the formula (7), wherein R ⁴ and R ~ ⁹ and agreement in the formula (M), are also the same preferred embodiment.

In the general formula (7), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride.

For example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe and the like, and AlCl, InCl, FeCl, TiCl _2, SnCl _2, SiCl _2, GeCl ₂ , etc., metal oxides such as TiO ₂ and V = O, and metal hydroxides such as Si (OH) ₂ .

Among them, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co and the like are used as metal atoms or metal compounds from the viewpoints of stability of the complex, spectroscopic characteristics, heat resistance, light resistance, , TiO 2 and V═O are preferable and Zn, Mg, Si, Pt, Pd, Cu, Ni, Co and V═O are more preferable and Zn, Co, V═O and Cu are more preferable , And Zn are particularly preferable.

In the general formula (7), R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

In the general formula (7), X ¹ may be any of groups capable of binding to Ma, and specifically concretely includes water, alcohols (e.g., methanol, ethanol, propanol) 1], and compounds described in Sakaguchi, Ueno, Keizo (1995, Nankodo), [2] (1996), [3] (1997), etc.). Among them, water, a carboxylic acid compound and an alcohol are preferable from the viewpoint of production, and water and a carboxylic acid compound are more preferable.

Examples of the "group for neutralizing the charge of Ma" represented by X ² in the general formula (7) include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group and a sulfonic acid group. Among them, , A halogen atom, a hydroxyl group, a carboxylic acid group and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.

In the general formula (7), X ¹ and X ² may combine with each other to form a 5-membered, 6-membered or 7-membered ring together with Ma. The 5-membered, 6-membered, and 7-membered rings to be formed may be a furan ring or an unsaturated ring. The 5-membered, 6-membered, and 7-membered rings may be composed of carbon atoms alone or may form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, and / or a sulfur atom.

As a preferred embodiment of the compounds represented by the general formula ^{(7), R 4 ~ R} 9 is a preferred embodiment one, each independently, formula (M) described in the description of R ⁴ ~ R ⁹ in, R ¹⁰ is formula and a preferred embodiment described in the description of R ¹⁰ in (M), Ma is Zn, Cu, Co, or V = O, X ¹ is water, or acid compounds, X ² is a hydroxy group, or a carboxylic acid group, and , And X ¹ and X ² may combine with each other to form a 5-membered or 6-membered ring.

The dipyrammethene metal complex compound represented by the general formula (8)

One suitable embodiment of the dye structure in the cation having a dye structure is a dye structure derived from a dipyrammethene metal complex compound represented by the following general formula (8). In the present invention, the following compounds form a cation structure. For example, Ma in formula (8) may form a metal cation structure such as zinc.

[Chemical Formula 21]

(Wherein R ¹¹ and R ¹⁶ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group, R ¹² to R ¹⁵ each independently represent a hydrogen atom or a substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and Ma represents a metal atom or a metal compound X ² and X ³ are each independently NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group), a nitrogen atom, Y ¹ and Y ² are each independently NR ^{c wherein} R ^c represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group ), A nitrogen atom or a carbon atom, R ¹¹ and Y ¹ may combine with each other to form a 5-membered, 6-membered or 7-membered ring, and R ¹⁶ and Y ² may combine with each other to form a 5-membered, 6-membered or 7-membered ring X ¹ represents a group capable of bonding to Ma, and a represents 0, 1, or 2.

Further, the dipyrammethene metal complex compound represented by the general formula (8) includes a tautomer.

Region to introduce a die pyrromethene metal complex compound represented by the general formula (8) in the structural units shown above in formula (A) ~ (D) are, without compromising the effect of the present invention is not particularly limited, R ¹¹ ~ R ¹⁷ , X ¹ , and Y ¹ to Y ² . Among these, from the viewpoint of synthesis suitability, R ¹¹ ~ R ¹⁶ and X ¹ of preferably introduced in any one, more preferably, R ^11, R ^13, R ¹⁴ and R ¹⁶ Insert according to any one of the , And more preferably, it is inserted in any one of R ¹¹ and R ¹⁶ .

In the case where the cation having a dye structure has an alkali-soluble group, it is preferable that any one or two or more substituents of R ¹¹ to R ¹⁷ , X ¹ , and Y ¹ to Y ² in the general formula (8) Can be used. Among these substituents, any one of R ¹¹ to R ¹⁶ and X ¹ is preferable, and any one of R ¹¹ , R ¹³ , R ^14, and R ¹⁶ is more preferable, and any one of R ¹¹ and R ¹⁶ is more preferable .

The dipyrammethene metal complex compound represented by the general formula (8) may have a functional group other than the alkali-soluble group as long as the effect of the present invention is not impaired.

In the general formula (8), R ¹² to R ¹⁵ are the same as R ⁵ to R ⁸ in the general formula (M), and preferred embodiments are also the same. R ¹⁷ is the same as R ¹⁰ in the formula (M), and preferred embodiments are also the same. Ma agrees with Ma in the general formula (7), and the preferable range is also the same.

More specifically, among R ¹² to R ¹⁵ in the general formula (8), examples of the R ¹² and R ¹⁵ include an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitryl group, an imide group and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group , An aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group and a carbamoyl group are particularly preferable.

R ¹³ and R ¹⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted Lt; / RTI &gt; Specific examples of the more preferable alkyl group, aryl group, and heterocyclic group include the specific examples of R &lt; ⁶ &gt; and R &lt; ⁷ &gt; in formula (M).

In the general formula (8), R ¹¹ and R ¹⁶ are preferably an alkyl group (preferably a straight chain, branched chain or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, An ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, (Preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, such as a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (Preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 hetero atoms And is, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 2-pyridyl, 2-benzothiazolyl (Preferably 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, for example, an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, (Preferably having 6 to 24 carbon atoms, more preferably 6 to 24 carbon atoms) such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, An aryloxy group having 1 to 18 carbon atoms such as a phenoxy group and a naphthyloxy group), an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably an alkylamino group having 1 to 18 carbon atoms, N, N-diethylamino group, N, N-diethylamino group, N, N-diethylamino group, N, N-diethylamino group, N, N-dimethylamino group, - dipropylamino group, N, N-dibutylamino , An N-methyl-N-ethylamino group), an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, and more preferably 6 to 18 carbon atoms such as a phenylamino group, a naphthylamino group, Phenylamino group), or a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-aminopyrrole group , 3-aminopyrazole, 2-aminopyridine group, 3-aminopyridine group).

R ¹¹ and R ¹⁶ are preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group or a heterocyclic amino group, more preferably an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, , An alkenyl group, and an aryl group are more preferable, and an alkyl group is particularly preferable.

In the general formula (8), when the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group or heterocyclic amino group represented by R ¹¹ and R ¹⁶ are further substitutable groups May be substituted with a substituent described in the section of Substituent Group A described later, and when they are substituted with two or more substituents, the substituents may be the same or different.

In the general formula (8), X ² and X ³ each independently represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom. Here, R represents a hydrogen atom, an alkyl group (preferably a straight chain, branched chain or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl group, ethyl group, (Such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, Preferably an alkenyl group having 2 to 24 carbon atoms and more preferably 2 to 12 carbon atoms such as a vinyl group, an allyl group and a 3-buten-1-yl group), an aryl group (preferably having a carbon number of 6 to 36 (Preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, , A 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, An imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group), an acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably a 2 to 18 carbon atoms, Ethylhexyl group, benzoyl group, cyclohexanoyl group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably an alkylsulfonyl group having 1 to 18 carbon atoms, for example, , An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably a carbon number of 6 to 18, such as a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, a cyclohexylsulfonyl group) A phenylsulfonyl group, a naphthylsulfonyl group).

In formula (8), Y ¹ and Y ² each independently represent NR ^C , a nitrogen atom, or a carbon atom, R ^C is the same as R of X ² and X ³ , and preferred embodiments are also the same .

In formula (8), R ¹¹ and Y ¹ are bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, A benzofuran ring, a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrazole ring, A pyridazine ring, a quinoline ring, a quinazoline ring), or a 7-membered ring (for example, a cyclohexane ring, a cyclopentadienyl ring, a cyclopentadienyl ring, Tetramine, tetramine, hexamethyleneimine).

In the general formula (8), R ¹⁶ and Y ² are bonded to each other to form a 5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring, a dioxolane ring, A benzofuran ring, a benzothiophene ring), a 6-membered ring (for example, a cyclohexane ring, a piperidine ring, a piperazine ring, a morpholine ring, A piperazine ring, a piperazine ring, a pyridazine ring, a quinoline ring, a quinazoline ring), or a 7-membered ring (for example, a cyclohexyl ring, a cyclopentadienyl ring, Heptane ring, hexamethyleneimine ring) may be formed.

In the case of 5-membered, 6-membered, and 7-membered rings formed by combining R ¹¹ and Y ¹ and R ¹⁶ and Y ² in the general formula (8) The substituents may be the same or different when they are substituted with two or more substituents.

In the general formula (8), R ¹¹ and R ¹⁶ are each independently preferably a monovalent substituent having a -Es' value of 1.5 or more, more preferably 2.0 or more, still more preferably 3.5 or more, and 5.0 Or more.

Here, the value of the three-dimensional parameter -Es' is a parameter indicating the three-dimensional bulky nature of the substituent, and is a structural active correlation between the structure activity correlation and the drug (JA Macphee, et al, Tetrahedron, Vol. 34, pp 3553-3562, Design, issued on February 20, 1986 (Kagakudojin)).

In the general formula (8), X ¹ represents a group capable of binding to Ma, specifically, a group similar to X ¹ in the general formula (7), and preferred embodiments are also the same.

a represents 0, 1 or 2;

As a preferred embodiment of the compounds represented by the general formula ^{(8), R 12 ~ R} 15 are, each independently, and the general formula The preferred that described in the description of of the R ⁵ ~ R ⁸ (M) embodiment, R ¹⁷ is the formula (M) is a preferred embodiment described in the R ¹⁰ of the description, Ma is Zn, Cu, Co, or V = O, X ² is NR a (R is a hydrogen atom, an alkyl group), a nitrogen atom, or oxygen atom, X ³ is NR (R is a hydrogen atom, an alkyl group) or an oxygen atom, Y ¹ is NR ^C (R ^C is a hydrogen atom, an alkyl group), a nitrogen atom or a carbon atom, Y ² is a nitrogen atom, , R ¹¹ and R ¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, X ¹ is a group bonded through an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5-membered or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5-membered or 6-membered ring.

As a more preferred embodiment of the compound represented by the general formula (8), R ¹² to R ¹⁵ are each independently a preferred embodiment described in the description of R ⁵ to R ⁸ in the compound represented by the general formula (M) R ¹⁷ is a preferred embodiment described in the description of R ¹⁰ in the general formula (M), Ma is Zn, X ² and X ³ are an oxygen atom, Y ¹ is NH, Y ² is a nitrogen atom, R ¹¹ and R ¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, X ¹ is a group bonded through an oxygen atom, and a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5-membered or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5-membered or 6-membered ring.

The molar extinction coefficient of the dipyrammethene metal complex compound represented by the general formula (7) and the general formula (8) is preferably as high as possible from the viewpoint of tinting strength. The maximum absorption wavelength? Max is preferably from 520 nm to 580 nm, more preferably from 530 nm to 570 nm, from the viewpoint of improving the color purity. By using the coloring composition of the present invention in this region, a color filter having good color reproducibility can be produced.

Further, the dye having a dye structure derived from a dipyramethine dye preferably has an absorbance of 1,000 times or more, more preferably 10,000 times or more, and more preferably 100,000 times or more of the absorbance at a maximum absorption wavelength (? Max) Or more. When the ratio is within this range, a color filter having a higher transmittance can be formed by using the coloring composition of the present invention, particularly when a blue color filter is produced. Further, the maximum absorption wavelength and the molar extinction coefficient are those measured by a spectrophotometer cary5 (manufactured by Varian).

The melting point of the dipyrammethene metal complex compound represented by the general formula (7) and the general formula (8) is preferably not too high from the viewpoint of solubility.

The dipyrammethene metal complex compounds represented by the general formulas (7) and (8) are described in U.S. Patent Nos. 4,774,339, 5,433,896, JP-A-2001-240761, 2002-155052, Japanese Patent Publication No. 3614586, Aust. J. Chem., 1965, 11, 1835-1845, J.H. Boger et al., Heteroatom Chemistry, Vol. 1, No. 5,389 (1990) and the like. Specifically, the method described in paragraphs 0131 to 0157 of Japanese Laid-Open Patent Publication No. 2008-292970 can be applied.

Specific examples of the dipyramethane coloring matter are shown below, but the present invention is not limited thereto. In the formulas, X represents an anion. In the present invention, any of the hydrogen atoms of the following dye structures is bonded to the polymer backbone.

[Chemical Formula 22]

Of the above specific examples, (PM-8) and (PM-10) are particularly preferable from the viewpoints of color characteristics and heat resistance.

<<< Carbonium coloring >>>

Among the carbonium dyes, triarylmethane dyes and xanthine dyes are preferred.

Triarylmethane dye

One of the aspects of the pigment structure according to the present invention is one having a partial structure derived from a triarylmethane dye (triarylmethane compound). The dye has, as a dye structure, a partial structure derived from a compound (triarylmethane compound) represented by the following general formula (TP).

The general formula (TP)

(23)

(Formula (TP) of, Rtp ¹ ~ Rtp ⁴ are, each independently, represent a hydrogen atom, alkyl group or aryl group. Rtp ⁵ is a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ is represents a represents a hydrogen atom, an alkyl group or an aryl group). Rtp ^6, Rtp ⁷ and Rtp ⁸ shows a substituent. a, b and c represents an integer of 0 ~ 4. a, b, and when c is 2 or more , Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be linked together to form a ring, and X ^- represents an anion structure.

For a preferable range and specific examples of the compound represented by the formula (TP), reference can be made to the description of paragraphs 0170 to 0178 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

The introduction site in the case of introducing a compound represented by formula (TP) into the structural unit represented by formula (A) is not particularly limited, but is preferably introduced at any one of Rtp ¹ to Rtp ¹⁰ .

Xanthan

A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a xanthine dye (xanthine compound). The dye has, as a dye structure, a partial structure derived from a xanthene compound represented by the following general formula (J).

&Lt; EMI ID =

(Wherein 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, X ^- represents an anion, X ^- does not exist, and at least one of R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ includes an anion.

The introduction site in the case of introducing a compound represented by the general formula (J) into the structural units represented by the above general formulas (A) to (D) is not particularly limited, but R ⁸¹ to R ⁸⁵ are introduced at any one site .

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

R ⁸¹ and R ⁸² in the general formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to form a 5-membered, 6-membered or 7-membered ring, , 6-membered or 7-membered unsaturated ring may be formed. When forming 5-, 6- substitutable due to the ring, the addition of, or 7-membered that is, there may be substituted with substituents described in the R ⁸¹ ~ R ⁸⁵ being, if it is substituted with two or more substituents, their substituents They may be the same or different.

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

In particular, it is preferable that R ⁸² and R ⁸³ are a hydrogen atom or a substituted or unsubstituted alkyl group, and R ⁸¹ and R ⁸⁴ are a substituted or unsubstituted alkyl group or a phenyl group. R ⁸⁵ is preferably a halogen atom, a 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 a xanthane skeleton represented by the general formula (J) can be synthesized by a method described in the literature. Specifically, Tetrahedron Letters, 2003, vol. 44, No. 23, pp. 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pp. 3097-3106, and the like can be applied.

X ^- it is, if showing a negative ion, it is possible to see the base of a case in which the counter anion to be described later of each (別) molecule, X ^- is not present, R ^81, R ^82, R ^83, R ^84, and R ⁸⁵ includes an anion, reference may be made to the description of the case where the opposite anion is within the same repeating unit.

Hereinafter, specific embodiments (first and second aspects) of the compound represented by the general formula (J) used in the present invention will be described, but the present invention is not limited thereto.

(First embodiment of the compound represented by the formula (J)

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

In general formula (2)

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

By such a constitution, solvent solubility of the coloring composition is further improved, and as a result, a coloring layer in which the surface shape unevenness is suppressed can be formed.

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

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

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

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

The heterocycle of the heterocyclic group may be a 5-membered or 6-membered ring, and they may be further condensed or not condensed. It may be an aromatic hetero ring or a non-aromatic hetero ring. Examples of the substituent include pyridine ring, pyrazine ring, pyridazin ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring, A thiazole ring, a thiazole ring, a thiazole ring, a thiazole ring, a thiazole ring, a benzothiazole ring, an isothiazole ring, a benzoisothiazole ring, A thiazole ring, an isoxazole ring, a benzoisooxazole ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, an imidazolidine ring, a thiazoline ring and the like. And may be an aromatic heterocycle or an aromatic heterocycle which may be substituted with at least one substituent selected from the group consisting of pyridine ring, pyrazine ring, pyridazin ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, A benzothiazole ring, a benzisothiazole ring and a thiadiazole ring, and may be a pyrazole ring, an imidazole ring, a benzoxazole ring, a thiadiazole ring, a pyrazole ring, a thiadiazole ring (1,3,4- Thiadiazole ring, 1,2,4-thiadiazole ring). They may have a substituent, and examples of the substituent are the same as those of the aryl group described later.

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

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

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

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

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

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

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

(Second embodiment of the compound represented by the general formula (J)

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

With such a constitution, the coloring composition can be obtained in which the spectral fluctuation at the time of alkali development is further suppressed, and a cured film excellent in heat resistance is obtained.

R ⁸¹ and R ⁸³ are each independently an aliphatic hydrocarbon group, which may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group, a propyl group or a butyl group, , n-propyl group, iso-propyl group, n-butyl group. R ⁸¹ and R ⁸³ may be the same or different, but may be the same. The alkyl group as R ⁸¹ and R ⁸³ may have a substituent, but may have a substituent.

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

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

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

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

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

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

Specific examples of the xanthene compound are shown below, but the present invention is not limited thereto. In the present invention, any of the hydrogen atoms of the following dye structures is bonded to the polymer backbone.

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(28)

[Chemical Formula 29]

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<< Azo dye >>

The azo dye may be appropriately selected from known azo dyes (for example, substituted azobenzene (AZ-4 to AZ-6 described later as specific examples)).

As azo dyes, azo dyes known as magenta dyes and yellow dyes can be applied. Of these, azo dyes represented by the following general formulas (d), (e), (g) , The general formula (I-2), and the general formula (V) are preferable.

<<< Magenta color >>>

The azo dye is suitably an azo dye represented by the following general formula (d) which is a magenta dye.

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In formula (d), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, , Or an arylsulfonyl group; A represents an aryl group or an aromatic heterocyclic group; Z ¹ to Z ³ each independently represent -C (R ⁵ ) = or -N =; and R ⁵ represents hydrogen An atom, or a substituent.

Each substituent in the general formula (d) will be described in detail.

In formula (d), R ¹ to R ⁴ each independently represents a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, Such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, (Preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms such as vinyl, allyl, 3-butene-1-yl), an aryl group (preferably having 6 to 36 carbon atoms , And more preferably an aryl group having 6 to 18 carbon atoms, such as phenyl or naphthyl), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, (Preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, such as acetyl, pivaloyl, 2-ethylhexyl, benzoyl, Cyclohexane oil), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (Preferably an aryloxycarbonyl group having 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 8 carbon atoms, more preferably 1 to 8 carbon atoms, A carbamoyl group having 2 to 6 carbon atoms, such as dimethylcarbamoyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, for example, Methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), or an arylsulfonyl group (Preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably a carbon number of 6 to 18, for example, phenylsulfonyl, naphthylsulfonyl).

R ¹ and R ³ are preferably each independently an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ² and R ⁴ are preferably each independently a hydrogen atom or an alkyl group.

When R ¹ to R ⁴ are substitutable groups, they may be substituted with, for example, the substituents described in the above group of substituent group A. When two or more substituents are present, the substituents may be the same or different .

R ¹ and R ^2, R ¹ and R ⁵ (Z ¹ or Z ² is -C (R ⁵⁾ = day time), R ³ and R ^4, R ³ and R ⁵ (Z ¹ is -C (R ⁵⁾ =) May be bonded to each other to form a 5-membered or 6-membered ring.

Z ¹ to Z ³ each independently represent -C (R ⁵ ) = or -N =, and R ⁵ represents a hydrogen atom or a substituent. As the substituent for R ⁵ , for example, the substituent described in the above-mentioned substituent group can be mentioned. When the substituent of R ⁵ is a further substitutable group, for example, the substituent may be substituted with the substituent described in the above-mentioned substituent group A. When the substituent is substituted with at least two substituents, the substituent may be the same or different .

As Z ¹ to Z ³ , preferably, Z ¹ is -N═, Z ² is -C (R ⁵ ) ═ or -N═, and Z ³ is -C (R ⁵ ) ═. More preferably, Z ¹ is -N═ and Z ² and Z ³ are -C (R ⁵ ) ═.

A represents an aryl group or an aromatic heterocyclic group. The aryl group and aromatic heterocyclic group of A may further have, for example, the substituents described in the above-mentioned substituents, and when they are substituted with two or more substituents, the substituents may be the same or different .

A is preferably an aromatic heterocyclic group. More preferably, it is an imidazole ring, a pyrazole ring, a triazole ring, a thiazole ring, an oxazole ring, a 1,2,4-thiadiazole ring, a 1,3,4-thiadiazole ring, a pyridine ring, Pyridine ring, pyrazine ring, benzopyrazole ring, benzothiazole ring and the like.

In the general formula (d), the moiety into which the polymerizable group involved in the polymerization (formation of the dye oligomer (A)) is introduced is not particularly limited, but from the viewpoint of compatibility, R ¹ , R ² and A It is preferably introduced into any one or two or more of them, more preferably R ¹ and / or A.

The azo dye represented by the general formula (d) is more preferably an azo dye represented by the following general formula (d ').

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In the general formula ^{(d '), R 1 ~} R 4 , the R ¹ ~ R ⁴ are synonymous with in the formula (d), the preferred range is also the same. Ra represents an electron-withdrawing group having a Hammett's substituent constant sigma p value of 0.2 or more, and Rb represents a hydrogen atom or a monovalent substituent. Rc represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group.

As the substituent represented by Rb, for example, the substituent described in the above group of substituent group A can be mentioned.

As the azo dye, an azo dye represented by the following general formula (e) which is a magenta dye is also suitable.

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In the general formula (e), R ¹¹ to R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ¹¹ and R ¹² , and R ¹⁵ and R ¹⁶ may be independently bonded to each other to form a ring.

Each substituent in the general formula (e) will be described in detail.

R ¹¹ to R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a halogen atom, an alkyl group having 1 to 30 carbon atoms (here, a saturated aliphatic group containing a cycloalkyl group and a bicycloalkyl group), an alkenyl group having 2 to 30 carbon atoms An alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, a cyano group, An aliphatic oxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an acyloxy group having 2 to 30 carbon atoms, a carbamoyloxy group having 1 to 30 carbon atoms, an aliphatic oxycarbonyloxy group having 2 to 30 carbon atoms, (Including an alkylamino group, an anilino group and a heterocyclic amino group) having 1 to 30 carbon atoms, an acylamino group having 2 to 30 carbon atoms, an aminocarbonylamino group having 1 to 30 carbon atoms, an amino group having 2 to 20 carbon atoms ~ 30 aliphatic oxycarbo An aryloxycarbonylamino group having 7 to 30 carbon atoms, a sulfamoylamino group having 0 to 30 carbon atoms, an alkyl or arylsulfonylamino group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms A sulfamoyl group having 0 to 30 carbon atoms, an alkyl or aryl sulfinyl group having 1 to 30 carbon atoms, an alkyl or aryl sulfonyl group having 1 to 30 carbon atoms, an acyl group having 2 to 30 carbon atoms, an aryloxy carbonyl group having 6 to 30 carbon atoms An aliphatic oxycarbonyl group having 2 to 30 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, an aryl or heterocyclic azo group having 3 to 30 carbon atoms, and an imide group, and each group may further have a substituent.

R ¹¹ and R ¹² are preferably each independently a hydrogen atom, a heterocyclic group or a cyano group, more preferably a cyano group.

R ¹³ and R ¹⁴ are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, more preferably a substituted or unsubstituted alkyl group.

R ¹⁵ and R ¹⁶ are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and more preferably a substituted or unsubstituted alkyl group.

In the general formula (e), there are no particular restrictions on the site into which the polymerizable group involved in the multimerization (formation of the dye oligomer (A)) is introduced. From the viewpoint of the compatibility with the synthesis, R ¹³ , R ¹⁵ and R ¹⁶ , more preferably R ¹³ and / or R ¹⁵ , and more preferably R ¹³ .

Of the above azo dyes, azo dyes represented by the general formula (e) are more preferable as the magenta dye.

- Yellow pigment -

Examples of the azo dye include azo dyes represented by the following general formula (g), general formula (I-1), general formula (I-2) and general formula (V) Can be suitably selected.

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In the general formula (g), R ³⁴ represents a hydrogen atom or a substituent, and R ³⁵ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Z ³⁰ and Z ³¹ each independently represent -C (R ³⁶ ) = or -N =, and R ³⁶ represents a hydrogen atom or a substituent. A ³¹ represents an aryl group or an aromatic heterocyclic group.

Each substituent in the general formula (g) will be described in detail.

R ³⁴ represents a hydrogen atom or a monovalent substituent, includes the substituents described in the above substituent group A, preferably an aryl group and a heterocyclic group, and more preferably a phenyl group.

R ³⁵ represents a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, (Preferably having 2 to 24 carbon atoms, more preferably 2 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, Is an alkenyl group having 2 to 12 carbon atoms such as vinyl, allyl, 3-butene-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms (For example, phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl, 2-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl) Is an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, such as acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkoxycarbonyl group (Preferably an alkoxycarbonyl group having from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, such as a methoxycarbonyl group or ethoxycarbonyl group), or a carbamoyl group (preferably having 1 to 10 carbon atoms, A carbamoyl group having 1 to 6 carbon atoms, for example, N, N-dimethylcarbamoyl).

Z ³⁰ and Z ³¹ each independently represent -C (R ³⁶ ) = or -N =, and R ³⁶ represents a hydrogen atom or a substituent. The substituent for R ³⁶ includes, for example, the substituents described in the above group of substituent group A. When the substituent of R ³⁶ is a further substitutable group, for example, the substituent may be substituted with the substituent described in the above-mentioned substituent group A. When the substituent is substituted with at least two substituents, the substituent may be the same or different .

As Z ³⁰ and Z ³¹ , preferably, Z ³⁰ is -N═ and Z ³¹ is -C (R ³⁶ ) =.

A ³¹ is synonymous with A in the general formula (d), and preferred embodiments are also the same.

In the formula (g), a large amount embodied region where the polymerizable group involved in (pigmentation of the oligomer (A)) introduced is not particularly limited, ve, from the viewpoint of synthesis suitability, R ³⁴ and / or A ³¹ is desirable.

(35)

In the general formulas (I-1) and (I-2), Ri ₁ , Ri ₂ and Ri ₃ each independently represent a monovalent substituent. a represents an integer of 0 to 5; When a is 2 or more, two adjacent Ri &_lt; ₁ &gt; may be connected to form a ring. b and c each independently represent an integer of 0 to 4; When b and c are 1 or more, they may be connected to adjacent two Ri &_lt; ₁ &gt; to form a ring. A ₃₂ represents the following general formula (IA), general formula (IB) or general formula (IC).

(36)

In the general formula (IA), R ₄₂ represents a hydrogen atom, an alkyl group or an aryl group. R ₄₃ represents a monovalent substituent. R ₄₄ represents a hydrogen atom, an alkyl group, or an aryl group.

(37)

In the general formula (IB), R ₄₄ and R ₄₅ each independently represent a hydrogen atom, an alkyl group or an aryl group. T represents an oxygen atom or a sulfur atom.

(38)

In the general formula (IC), R ₄₆ represents a hydrogen atom, an alkyl group, or an aryl group. R ₄₇ represents a monovalent substituent.

Examples of the monovalent substituent represented by Ri ₁ , Ri ₂ and Ri _{3 in the} general formulas (I-1) and (I-2) include the substituents exemplified in the above-mentioned substituent group A. Specific examples of the monovalent substituent include an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as methyl, ethyl, Cyclohexyl, 1-adamantyl), an aryl group (preferably having 6 to 36 carbon atoms, more preferably 6 to 36 carbon atoms, Preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl, naphthyl or sulfonamido group), an alkenyl group (having 1 to 10 carbon atoms, more preferably a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, (Preferably an alkylsulfamoyl group having 1 to 10 carbon atoms), and particularly preferably an alkenyl group having 1 to 10 carbon atoms, such as a vinyl group, an allyl group, a perylene group, a geranyl group, an oleyl group, An alkyl group having 1 to 5 carbon atoms and an alkylsulfamoyl group having 1 to 10 carbon atoms are preferable. a is preferably 1 to 3. b and c are preferably 1 to 3.

In the general formula (IA), R ₄₂ represents a hydrogen atom, an alkyl group or an aryl group, and particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group. As the monovalent substituent represented by R ₄₃ , substituents exemplified in the group of substituent group A can be exemplified, and a cyano group and a carbamoyl group are particularly preferable. R ₄₄ represents a hydrogen atom, an alkyl group, or an aryl group, particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group.

In the general formula (IB), T represents an oxygen atom or a sulfur atom, preferably an oxygen atom. R ₄₄ and R ₄₅ each independently represent a hydrogen atom, an alkyl group or an aryl group, and particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group.

In the general formula (IC), R ₄₆ represents a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group. As the monovalent substituent represented by R ₄₇ , substituents exemplified in the group of substituent group A are exemplified, and hydrogen atom, alkyl group and aryl group are preferable, and alkyl group having 1 to 5 carbon atoms and phenyl group are particularly preferable.

[Chemical Formula 39]

In the general formula (V), Mv represents Cr or Co. Rv ₁ represents an oxygen atom or -COO-. Rv ₂ and Rv ₃ each independently represent a hydrogen atom, an alkyl group or an aryl group. v represents an integer of 0 to 4; Rv ₄ represents a monovalent substituent. When v is greater than or equal to 2, the Rv ₄ between adjacent are connected to each other to form a ring.

Rv ₂ and Rv ₃ are preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group. As the monovalent substituent represented by Rv ₄ , there can be mentioned substituents exemplified in the above substituent group A, particularly preferably an alkyl group, an aryl group, a nitro group, a sulfamoyl group and a sulfo group, and an alkyl group having 1 to 5 carbon atoms , A phenyl group and a nitro group are most preferable.

Among the azo dyes described above, the yellow dye is preferably an azo dye represented by the formula (I-1), the formula (I-2) and the formula (V).

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

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(41)

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(AZ-7), (AZ-9), (AZ-11), (AZ-13), (AZ-14) (AZ-16), (AZ-17), (AZ-19), (AZ-20), (AZ-21) and (AZ-22).

<<< Cyanine color >>>

One of the aspects of the cation having a dye structure according to the present invention is one having a partial structure derived from a cyanine dye (a cyanide compound). For details of these, reference can be made to the description of paragraphs 0191 to 0201 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

<<< Subphthalocyanine pigment >>>

One aspect of the cation having a dye structure according to the present invention is one having a subphthalocyanine pigment structure. For details of these, reference can be made to the description of paragraphs 0242 to 0250 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

<< Squarylium pigment >>

The cation having a dye structure used in the present invention may have a squarylium dye structure. For details of these, reference may be had to the description of paragraphs 0202 to 0223 of Japanese Laid-Open Patent Publication No. 2013-28764, the contents of which are incorporated herein by reference.

The dye of the present invention may be substituted with a substituent selected from Substituent Group A below in the dye structure as long as it does not deviate from the object of the present invention.

Substituent group A:

The substituent which the dye may have includes a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, An alkoxy group, an aryloxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an amino group (including an alkylamino group and an anilino group), an acylamino group, an aminocarbonylamino group, An alkylsulfonylamino group, an alkylsulfonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, A silyl group, and the like. The details will be described below.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms (Preferably 3 carbon atoms) such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2- chloroethyl, 2-cyanoethyl, A substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms such as cyclohexyl and cyclopentyl and is preferably a polycycloalkyl group such as a bicycloalkyl group Or a substituted or unsubstituted bicycloalkyl group such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] Preferred examples thereof include a monocyclic cycloalkyl group, a bicyclic Cycloalkyl group, monocyclic cycloalkyl group being particularly preferred),

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

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

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

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

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

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

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

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

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

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

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

<<< counter negative ion >>>

When the dye structure used in the present invention has a cation structure, the counter anion may be present in the same repeating unit of the dye multimer or may be other than the same repeating unit. The presence of the counter anion in the same repeating unit refers to a case in which a cation and an anion are bonded through a covalent bond in a repeating unit having a pigment structure. On the other hand, the same repeating unit disturbance refers to cases other than the above. For example, the case where the cation and the anion are not bonded through a covalent bond but exists as a separate compound, and the case where the cation and the anion are included as independent repeating units of the dye multimer, respectively.

The anion in the present invention is preferably an unconjugated anion, and the non-nucleophilic anion may be an organic anion, an inorganic anion, or an organic anion. Examples of the counter anion used in the present invention include known non-nucleophilic anions described in Japanese Patent Application Laid-Open No. 2007-310315, paragraph No. 0075, the contents of which are incorporated herein by reference. Here, the term &quot; non-nucleophilic &quot; means a property of not attacking the pigment by nucleation.

If the counter anion is in the same repeat unit

The first embodiment of the anion in the present invention is a case where the opposite anion is present in the same repeating unit, specifically, a case in which a cation and an anion are bonded through a covalent bond in a repeating unit having a dye structure .

To, the following structures to and represented by a general formula (A1) at least one member selected from the structure represented by the general formula (A2) preferably, and ^- as the anion portion of the _{^{case, -SO 3 -, -COO -,}} -PO 4 Is more preferably at least one selected from the structure represented by the general formula (A1) and the structure represented by the following general formula (A2).

In formula (A1)

(44)

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

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

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

In general formula (A1-1)

[Chemical Formula 45]

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

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

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

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

In general formula (A2)

(46)

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

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

In the present embodiment, particularly, when the skeleton of the dye multimer is represented by the structural unit represented by the general formula (A), a case where a part of L ₁ includes a moiety represented by the general formula (A1) is a preferable example . Specific examples of such a case include (a-xt-1), (a-xt-5) and (a-xt-6) in the examples of repeating units having a dye structure described below.

In the present embodiment, the skeleton of the dye multimer used in the present invention includes a structural unit represented by the general formula (B). (B-dp-1), (B-mp-1), (B-xt-1) and (B-xt-2) in the examples of the repeating units having a dye structure .

If the counter anion is a star molecule

The second embodiment of the anion in the present invention is a case where the opposite anion is out of the same repeating unit and the cation and the anion are not bonded through a covalent bond and exist as a star molecule.

Examples of the anion in this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion and the like, and non-nucleophilic anions are preferable.

The counter anion of the non-nucleophilic nature may be an organic anion, an inorganic anion, or an organic anion. Examples of the counter anion used in the present invention include known non-nucleophilic anions described in Japanese Patent Application Laid-Open No. 2007-310315, paragraph No. 0075, the contents of which are incorporated herein by reference.

Preferably, the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion, tetra aryl borate anions, B ^- (CN) _n1 (OR ^a) _4-n1 (R ^a represents an alkyl group having 1 to 10 carbon atoms or aryl group having a carbon number of 6 ~ 10, n1 represents 1 to 4) and _{^{PF n2 R P (6-n2}} ) - (R P represents a fluorinated alkyl group having a carbon number of 1 ~ 10, n2 is an integer of 1-6 , And more preferably selected from bis (sulfonyl) imide anion, tris (sulfonyl) methyl anion and tetraaryl borate anion, and more preferably bis (sulfonyl) imide anion. By using such an anion having an acetonuclear nature, the effect of the present invention tends to be more effectively exerted.

As the bis (sulfonyl) imide anion which is an anion of a non-nucleophilic group, a structure represented by the following general formula (AN-1) is preferable.

(47)

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

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

As the tris (sulfonyl) methyl anion which is an opposite anion of an acetyl nucleus, a structure represented by the following general formula (AN-2) is preferable.

(48)

(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 each independently are the same as X ¹ and X ² , and the preferable range is also synonymous.

The tetraarylborate anion, which is an anion of an acetonuclear nature, is preferably a compound represented by the following formula (AN-5).

(49)

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

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

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

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

The counter anion of the non- _nucleophilic group may be a group of the formula: -B (CN) _n1 (OR ^a ) _{4 -n} 1 wherein R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, ). 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 more preferably -PF ₆ R ^P _{(6-n 2)} ^- (wherein R ^P is a fluorinated alkyl group having 1 to 10 carbon atoms and n 2 is an integer of 1 to 6). R ^P is preferably an alkyl group having 1 to 6 carbon atoms and more preferably a fluorine atom having 1 to 4 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

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

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

The dye multimer of the present invention may contain only one kind of non-nucleophilic counter anion or two or more kinds of non-nucleophilic counter anions.

Hereinafter, specific examples of the counter-nucleophilic counter anion used in the present invention are shown, but the present invention is not limited thereto.

(50)

(51)

(52)

(53)

In the second embodiment, the anion may be a mass of anion. As the multimer in this case, a multimer containing a repeating unit containing an anion and containing no repeating unit derived from a dye structure containing a cation is exemplified. Here, as the repeating unit containing an anion, a repeating unit containing an anion described in the third embodiment to be described later may be mentioned as a preferable example. Further, the multimer containing an anion may have a repeating unit other than the repeating unit containing an anion. As such a repeating unit, other repeating units which may be contained in the dye multimer used in the present invention to be described later are exemplified as preferable examples.

When cations and anions are included in other repeating units of the dye multimer

The third embodiment of the present invention refers to a case where cations and anions are included in independent repeating units of a dye multimer.

In the case of the present embodiment, the anion may be present in the side chain of the dye multimer, may be contained in the main chain, or may have a counter anion in both the main chain and the side chain. Preferably, it is a side chain.

Preferable examples of the repeating unit containing an anion include repeating units represented by the formula (C) and repeating units represented by the formula (D).

In the general formula (C)

(54)

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

In the general formula (C), X ¹ represents a main chain of a repeating unit, and usually represents a linking group formed by a polymerization reaction, and examples thereof include (meth) acrylic, styrene, ) Acrylic type and styrene type is more preferable, and (meth) acrylic type is more preferable. In addition, the parts indicated by two * are repeated units.

When L ¹ represents a divalent linking group, an 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), an arylene group having 6 to 30 carbon atoms (a phenylene group, ), A heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O) -, -CO-, -NR-, -CONR-, -OC-, -SO-, -SO ₂ -, and a linking group combining two or more of them. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In particular, L ¹ represents a single bond or an alkylene group having 1 to 10 carbon atoms (preferably - (CH ₂ ) n - (n is an integer of 5 to 10) and an arylene group having 6 to 12 carbon atoms A phenylene group, a naphthalene group), -NH-, -CO ₂ -, -O- and -SO ₂ -.

Specific examples of X ^1, examples of X ¹ in the general formula (A) may be mentioned as a preferable example.

In general formula (D)

(55)

(In the general formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group.) Anion represents the opposite anion.

In the formula (D), when L ² and L ³ represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH═CH-, -O-, -S-, -C (= O) -, -CO ₂ -, -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ - and a linking group combining two or more thereof. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

L ² is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group). The arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.

L ³ is preferably a group formed by a combination of an arylene group (particularly a phenylene group) having 6 to 12 carbon atoms and -O-, and at least one arylene group having 6 to 12 carbon atoms is preferably substituted with a fluorine atom.

As the counter anion, the anion moiety described as the case where the opposite anion is present in the same repeating unit is exemplified as a preferable anion.

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

(56)

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

(57)

(58)

[Chemical Formula 59]

(60)

(61)

Examples of the repeating unit having a dye structure preferably used in the present invention are shown below. It is needless to say that the present invention is not limited to these. X ^- represents a counter anion. It should be noted that some Xs are shown in a state in which the anion structure is not dissociated, but it is needless to say that the dissociation state is also included in the present invention.

(62)

(63)

&Lt; EMI ID =

(65)

(66)

(67)

(68)

(69)

<< Other functional groups and repeating units >>

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

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

As other repeating units, repeating units containing at least one of a polymerizable group and an alkali-soluble group (preferably, an acid group) are exemplified.

That is, the pigment multimer of the present invention may have other repeating units other than the repeating units represented by the above general formulas (A) to (C). The other repeating units may be contained in only one kind or two or more kinds in one coloring matter multimer.

The dye multimer of the present invention may contain other functional groups in the dye multimer represented by the above general formulas (A) to (D). The details of these will be described below.

<<< Polymerizable group possessed by a dye multimer >>>>

The dye multimer of the present invention preferably contains a polymerizable group. The polymerizable group may be contained only in one kind or in two or more kinds.

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

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

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

The polymerizable group is preferably contained as a repeating unit having a polymerizable group in the dye oligomer, more preferably as a repeating unit having an ethylenically unsaturated bond. That is, an example of a preferred embodiment of the dye multimer of the present invention is a mode in which the dye multimer contains a repeating unit including a dye monomer and a repeating unit having a polymerizable group, wherein the repeating unit containing a dye monomer and the ethylenically unsaturated It is more preferable to contain a repeating unit having a bond.

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

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

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

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

As the unsaturated bond-containing isocyanate compound in the method of reacting the hydroxyl group or amino group of the dye oligomer (b) with the unsaturated bond-containing isocyanate compound, there may be mentioned 2-isocyanatoethyl methacrylate, Isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Of these, 2-isocyanatoethyl methacrylate is preferable because of its crosslinkability and storage stability Is preferable. As the reaction conditions, known conditions can be used.

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

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

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

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

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

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

The amount of the polymerizable group of the dye multimer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and particularly preferably 0.3 to 1.0 mmol based on 1 g of the colorant multimer.

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

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

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

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(71)

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

<<< Alkali-soluble group possessed by the dye oligomer >>>>

Examples of the alkali-soluble group which may be contained in the dye multimer in the present invention are an acid group, and examples of the acid group include a carboxylic acid group, a sulfonic acid group and a phosphoric acid group.

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

When the dye multimer used in the present invention has an acid group, the acid value of the dye multimer of the present invention is preferably 0.5 to 1.50 mmol / g, more preferably 0.5 to 1.0 mmol / g.

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

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

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

The dye multimer used in the present invention is a repeating unit containing an alkali-soluble group, which is a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains on the side chain (hereinafter referred to as "(b) repeating unit" May be included).

The number of repeating units of the alkyleneoxy chain in the repeating unit (b) 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.

In the present invention, the repeating unit of 2 to 20 unsubstituted alkyleneoxy chains may contain only one type of alkyleneoxy group, or two or more types may be contained.

In the present invention, the repeating unit (b) is preferably represented by the following general formula (P).

In general formula (P)

(72)

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

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

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

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

(b) a repeating unit having a repeating unit of 2 to 20 unsubstituted alkyleneoxy chains in the side chain is preferably 2 to 20 mol% of all repeating units constituting the colorant multimer, and 5 To 15 mol% is more preferable.

Hereinafter, examples of the repeating unit (b) usable in the present invention are shown, but it is needless to say that the present invention is not limited thereto.

(73)

&Lt; EMI ID =

<<< Structural unit having at least one of structures represented by formulas (1) to (5) >>>

The dye multimer used in the present invention may have at least one of the structures represented by the formulas (1) to (5) in the same molecule. With such a constitution, when the cured film is produced, the exposure sensitivity and the light resistance can be improved. Here, the structure represented by the formulas (1) to (5) functions as a light stabilizer, thereby contributing to improvement of exposure sensitivity and light resistance. Further, the adhesion can be improved. In addition, generation of development residue can be suppressed. This mechanism is presumed. However, by using a pigment multimer having a pigment structure and at least one of the structures represented by the formulas (1) to (5) in the same molecule, The distance of the appearing structure becomes closer. As a result, it is considered that the exposure sensitivity and the light resistance can be improved more effectively.

The structure represented by the formula (1) is generically referred to as a hindered amine system. The structure represented by the formula (2) is generically referred to as a hindered phenol system. The structure represented by the formula (3) is collectively referred to as a benzotriazole system. The structure represented by the formula (4) is generically referred to as a hydroxybenzophenone system. The structure represented by the formula (5) is generically referred to as a triazine system.

(75)

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an oxy radical. R ² and R ³ each independently represent an alkyl group having 1 to 18 carbon atoms. R ² and R ³ may bond to each other to represent an aliphatic ring having 4 to 12 carbon atoms. "*" Represents the bonding of the structure represented by the formula (1) and the polymer skeleton.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an oxy radical, and is preferably an alkyl group having 1 to 18 carbon atoms.

The alkyl group having 1 to 18 carbon atoms may be straight chain, branched chain or cyclic, and is preferably straight-chain. The number of carbon atoms of the alkyl group having 1 to 18 carbon atoms is preferably 1 to 12, more preferably 1 to 8, further preferably 1 to 3, particularly preferably 1 or 2. In particular, the alkyl group having 1 to 18 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group.

The carbon number of the aryl group may be 6 to 18, may be 6 to 12, or may be 6 to 6. Specific examples thereof include a phenyl group.

When R ¹ in the formula (1) represents an alkyl group or an aryl group having 1 to 18 carbon atoms, the alkyl group or aryl group having 1 to 18 carbon atoms may have a substituent or may be unsubstituted. As the substituent which may be contained, a substituent selected from the above-mentioned substituent group A can be mentioned.

In the formula (1), R ² and R ³ each independently represent a methyl group or an ethyl group, and a methyl group is preferable. R ² and R ³ may bond to each other to represent an aliphatic ring having 4 to 12 carbon atoms.

In the formula (1), "*" represents a bond between the structure represented by the formula (1) and the polymer backbone. The bonding hands may be bonded to the polymer backbone directly or via a linking group, or may be bonded to the above-mentioned pigment structure directly or via a linking group. In particular, "*" in the formula (1) is preferably bonded to the polymer skeleton directly or via a linking group.

Specific examples of the structure represented by the formula (1) are shown below, but the present invention is not limited thereto. In the structure shown below, "*" represents the bonding of the structure represented by formula (2) and the polymer backbone.

[Formula 76]

[Formula 77]

In the formula (2), R ⁴ represents an alkyl group or an aryl group having 1 to 18 carbon atoms represented by the following formula (2A). And each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. "*" Represents the combined hand of the structure represented by formula (2) and the polymer skeleton.

In the formula (2), R ⁴ represents the formula (2A), the alkyl group or the aryl group having 1 to 18 carbon atoms, and is preferably represented by the formula (2A). The alkyl group having 1 to 18 carbon atoms and the aryl group are the same as the alkyl group and aryl group having 1 to 18 carbon atoms described for R ¹ in formula (1). In addition, "*" is a combination hand and an agreement described in equation (1).

(78)

In the formula (2A), each R ⁶ independently represents an alkyl group having 1 to 18 carbon atoms. "*" Represents the combined hand of the structure represented by the formula (2A) and the structure represented by the formula (2).

In the formula (2A), R ⁶ is the same as the alkyl group having 1 to 18 carbon atoms described for R ¹ in the formula (1). In addition, "*" is a combination hand and an agreement described in equation (1).

Specific examples of the structure represented by the formula (2) are shown below, but the present invention is not limited thereto. In the structure shown below, "*" represents the bonding of the structure represented by formula (2) and the polymer backbone.

(79)

(80)

In the formula (3), R ⁷ represents an alkyl group having 1 to 18 carbon atoms; n1 represents an integer of 0 to 3; if n1 is 2 or 3, each R ⁷ is, it may be the same or different. "*" Represents the combined hand of the structure represented by formula (3) and the polymer skeleton.

In the formula (3), R ⁷ is the same as the alkyl group having 1 to 18 carbon atoms described for R ¹ in the formula (1).

In the formula (3), n1 represents an integer of 0 to 3, preferably an integer of 0 to 2, and 0 or 1 is preferable.

In Equation (3), "*" is the combined hand and agreement described in Equation (1).

Specific examples of the structure represented by the formula (3) are shown below, but the present invention is not limited thereto. In the following structures, "*" represents the bonding of the structure represented by formula (3) and the polymer backbone.

[Formula 81]

(82)

In formula (4), R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 18 carbon atoms. n2 represents an integer of 0 to 3; n3 represents an integer of 0 to 4; When n2 is 2 or 3, each R ⁸ may be the same or different. when n3 represents an integer of 2-4, and each R ⁹ is, it may be the same or different. "*" Represents the combined hand of the structure represented by the formula (4) and the polymer skeleton.

In the formula (4), R ⁸ and R ⁹ are the same as the alkyl group having 1 to 18 carbon atoms described for R ¹ in the formula (1).

In the formula (4), n2 represents an integer of 0 to 3, preferably an integer of 0 to 2, and 0 or 1 is preferable.

In the formula (4), n3 represents an integer of 0 to 4, preferably an integer of 0 to 2, and 0 or 1 is preferable.

In Equation (4), "*" is the combined hand and agreement described in Equation (1).

Specific examples of the structure represented by the formula (4) are shown below, but the present invention is not limited thereto. In the structure shown below, "*" represents the bonding of the structure represented by the formula (4) and the polymer backbone.

(83)

(84)

In the formula (5), R ¹⁰ to R ¹² each independently represent an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. n4 to n6 each independently represent an integer of 0 to 5; n7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1. "*" Represents the combined hand of the structure represented by formula (5) and the polymer skeleton.

When R ¹⁰ in the formula (5) represents an alkyl group having 1 to 18 carbon atoms, it is preferably an alkyl group having 1 to 3 carbon atoms, which is the same as the alkyl group having 1 to 18 carbon atoms described for R ¹ in formula (1) desirable. When R ¹⁰ represents an alkoxy group having 1 to 8 carbon atoms, the carbon number of the alkoxy group is preferably 1 to 6, more preferably 1 to 5, and further preferably 1 to 4.

R ¹⁰ in the formula (5) may further have a substituent. As the substituent which may be contained, a substituent selected from the above-mentioned substituent group A can be mentioned.

N4 in the formula (5) represents an integer of 0 to 5, preferably an integer of 1 to 4, and preferably 2 or 3. When n4 represents an integer of 2 to 5, each R ¹⁰ may be the same or different.

R ¹¹ in the formula (5) agrees with R ¹⁰ in the formula (5), and the preferable range is also the same.

N5 in the formula (5) represents an integer of 0 to 5, preferably an integer of 1 to 3, and preferably 1 or 2. When n5 represents an integer of 2 to 5, each R &lt; ¹¹ &gt; may be the same or different.

R ¹² in the formula (5) agrees with R ¹⁰ in the formula (5), and the preferable range is also the same.

N6 in the formula (5) represents an integer of 0 to 5, preferably an integer of 0 to 3, and 0 or 1 is preferable. When n6 represents an integer of 2 to 5, each R ¹² may be the same or different.

N7 to n9 in the formula (5) each independently represent 0 or 1, and at least one of n7 to n9 represents 1. In particular, it is preferable that only n7 represents 1, only n8 and n9 represent 1, or n7, and only one of n8 and n9 represents 1.

In Equation (5), "*" is the combined hand and agreement described in Equation (1).

Specific examples of the structure represented by the formula (5) are shown below, but the present invention is not limited thereto. In the structure shown below, "*" represents the bonding bond between the structure represented by the formula (5) and the polymer backbone.

(85)

The constituent unit having at least one of the structures represented by the formulas (1) to (5) of the dye multimer used in the present invention is preferably represented by the following formula (E).

(E)

&Lt; EMI ID =

In the general formula (E), X ³ is synonymous with X ₁ in the general formula (A). L ⁴ is synonymous with L ₁ in the general formula (A). Z ¹ represents a structure represented by the above-mentioned formulas (1) to (5).

Specific examples of the structural unit having at least one of the structures represented by the formulas (1) to (5) are shown below, but the present invention is not limited thereto.

[Chemical Formula 87]

The pigment multimer may not have a constitutional unit having at least one of the structures represented by the formulas (1) to (5), but when having the constitutional unit represented by the formula (1) ) To (5) is preferably from 0.5 to 20% by mass, more preferably from 1 to 10% by mass, and particularly preferably from 1 to 5% by mass.

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

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

Specific examples of the repeating unit having an alkali-soluble group and other functional groups that the dye multimer can have are shown, but the present invention is not limited thereto.

[Formula 88]

(89)

(90)

[Formula 91]

&Lt; EMI ID =

&Lt; EMI ID =

The weight average molecular weight of the dye multimer is preferably from 3,000 to 30,000, more preferably from 5,000 to 25,000.

The ratio [Mw / (Mn)] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the pigment multimer is preferably 1.0 to 2.0, more preferably 1.1 to 1.8, To 1.5 is particularly preferable.

The glass transition temperature (Tg) of the colorant multimer according to the present invention is preferably 50 占 폚 or higher, and more preferably 100 占 폚 or higher. The 5% weight reduction temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C or higher, more preferably 150 ° C or higher, and even more preferably 200 ° C or higher. In this region, when the coloring composition of the present invention is applied to the production of a color filter or the like, the concentration change due to the heating process can be reduced.

When the polymeric multimer used in the present invention contains a repeating unit having a dye structure and another repeating unit, it is preferable that the polymer is a random polymer of a polymerizable compound other than the dye. When the polymer is a random polymer, the dye structure is randomly present in the dye multimer, and the effect of the present invention is more effectively exhibited.

It is preferable that the absorption coefficient per unit weight of the colorant multimer according to the present invention (hereinafter referred to as 竜 ', 竜' = 竜 / average molecular weight, unit: L / g 揃 cm) is 30 or more, More preferably 100 or more. Within this range, it is possible to manufacture a color filter having good color reproducibility when a color filter is manufactured by applying the coloring composition of the present invention.

The molar extinction coefficient of the colorant multimer used in the coloring composition of the present invention is preferably as high as possible from the viewpoint of coloring power.

The reduced viscosity of the colorant multimer used in the coloring composition of the present invention is preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and still more preferably 6.0 to 7.0 from the viewpoint of mordanting. The reduced viscosity can be measured using, for example, a Ubero type viscometer.

1.0 to 1.8

The pigment multimer according to the present invention is preferably a compound dissolved 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- , Aromatic hydrocarbon (for example, toluene, xylene, etc.), and it is preferable that the solvent is dissolved in 1 mass% to 50 mass%, more preferably 5 mass% to 40 mass % Or less, more preferably 10 mass% or more and 30 mass% or less. When the coloring composition of the present invention is applied to the production of a color filter or the like in this region, it is possible to reduce a drop in concentration due to a suitable application surface shape or dissolution after the application of the coloring.

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

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

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

<Coloring composition>

Next, the coloring composition of the present invention will be described. The coloring composition of the present invention is preferably used for forming a colored layer of a color filter. The coloring composition used in the present invention may contain a polymerizable compound and may also contain a photopolymerization initiator and a pigment.

For example, in the case of forming a colored layer by photoresist, the coloring composition of the present invention is preferably a composition comprising the pigment multimer, the polymerizable compound, the alkali-soluble resin, the photopolymerization initiator and the pigment of the present invention. Further, it may contain components such as a surfactant and a solvent.

In the case of forming a colored layer by dry etching, a composition comprising the pigment multimer, the polymerizable compound, the photopolymerization initiator and the pigment of the present invention is preferable. Further, it may contain components such as a surfactant and a solvent.

The details of these will be described below.

<Polymerizable compound>

The coloring composition of the present invention contains a polymerizable compound.

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

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

More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, 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, 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, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

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

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 at normal pressure. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and (meth) acrylate, Japanese Examined Patent Publication 48 (Meth) acrylate as described in JP-A-41708, JP-A-50-6034, JP-A-51-37193 Japanese Unexamined Patent Publication No. 48-64183, Japanese Unexamined Patent Publication No. 49-43191, Japanese Unexamined Patent Publication (Kokai) No. 52-30490, reaction between epoxy resin and (meth) acrylic acid Polyfunctional acrylates and methacrylates such as epoxy acrylates as products, and mixtures thereof.

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

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

As the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher at normal pressure, the compounds described in paragraphs [0254] to [0257] of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

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

(94)

&Lt; EMI ID =

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

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

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

Further, in JP-A 10-62986, ethylene oxide or propylene oxide is added to the polyfunctional alcohol represented by the general formulas (1) and (2) together with the specific examples thereof and then (meth) acrylated The compound may also be used as a polymerizable compound.

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kayaku Co., (KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) (Trade name: A-DPH-12E, manufactured by Nippon Kayaku K.K.) and ethylene oxide-modified di (ethylene glycol) diacrylate, ethylene glycol-modified dipentaerythritol hexaacrylate A structure in which a propylene glycol residue is interposed is preferable. These oligomer types can also be used.

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

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

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

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

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

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

&Lt; EMI ID =

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).

[Formula 97]

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.

(98)

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

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (m = 1 in the above formulas (1) to (3) the number of groups represented by the formula (2) = 2, R ^1, all of the compounds), DPCA-30 (the same formula, m = 1, equation (2) of the group represented by = 3, R ¹ are both hydrogen hydrogen atoms DPCA-120 (m = 2 in the same formula), DPCA-60 (the same formula, m = 1, the number of groups represented by formula (2) = 6 and R ¹ are all hydrogen atoms) The number of groups represented by formula (2) = 6, and R ¹ are all hydrogen atoms).

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

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

[Formula 99]

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

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

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

In the general formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

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

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

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

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

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

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

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

(A), (b), (f), (f), (f) and (f) , (e) and (f) are preferable.

(100)

(101)

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

Examples of the polymerizable compound include those described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293, and JP-A-2-16765 Such as urethane acrylates as disclosed in Japanese Patent Publication No. 58-49860, Japanese Examined Patent Publication No. 56-17654, Japanese Examined Patent Publication No. 62-39417, Japanese Examined Patent Publication No. 62-39418 Yutein compounds having an ethylene oxide skeleton are also suitable. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 By using the polymerizable compounds, a curable composition having an extremely high photosensitive speed can be obtained.

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

JER-827, JER-834, JER-1001, JER-1002, and JER-1003 as the bisphenol A type epoxy resin having an epoxy group as the cyclic ether (epoxy, oxetane) (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (manufactured by DIC Corporation), and the like, JER-807, JER-4004, JER-4005, JER-4007 and JER-4010 (manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 830, EPICLON 835 152, JER-154, JER-157S70, and JER-157 as a phenol novolak type epoxy resin, and the like. EPICLON N-770, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation), and the like as cresol novolak type epoxy resin , EPICLON N-660, EPICLON N-660, EPICLON N-660, EPICLON N-670, EPICLON N-670, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation) as an aliphatic epoxy resin, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) Epoxy-4- (2-oxiranyl) benzoic acid of 2,2-bis (hydroxymethyl) -1-butanol, ) Cyclohexane adduct), EPOLEAD PB 3600, PB 4700 (manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX- (Manufactured by ADEKA Corporation), NC-2000 (manufactured by Nippon Steel Chemical Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP- NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA) and JER-1031S (manufactured by Japan Epoxy Resin Co., Ltd.). Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

The details of the structure, the use of the single polymerizable compound, the combination thereof, and the amount of the polymerizable compound can be arbitrarily set in accordance with the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferable, and in many cases, a bifunctionality or more is preferable. Further, from the viewpoint of enhancing the strength of the cured film formed by the coloring composition, it is preferable to use trifunctional or more functional groups and the number of functional groups different from each other (e.g., acrylic acid ester, methacrylic acid ester, styrene series compound, vinyl ether group compound) A method of controlling both sensitivity and strength is also effective. It is also preferable to use a polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths from the viewpoint that the developability of the colored composition can be controlled and an excellent pattern forming ability can be obtained.

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

The content of the polymerizable compound in the coloring composition of the present invention is preferably 0.1% by mass to 90% by mass, more preferably 1.0% by mass to 60% by mass relative to the total solid content in the coloring composition, And particularly preferably from 40% by mass to 40% by mass.

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

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 alkane thiol compound, particularly preferably a compound having a structure represented by the following general formula (I).

The compound of formula (I)

&Lt; EMI ID =

(Wherein n represents an integer of 2 to 4, and L represents a linking group having 2 to 4 valences.)

In the general formula (I), 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 (II) to (IV), and compounds represented by (II) are particularly preferable. These polyfunctional thiols can be used singly or in combination.

&Lt; EMI ID =

The blending amount of the polyfunctional thiol in the composition of the present invention is preferably 0.3 to 8.9% by weight, more preferably 0.8 to 6.4% by weight, based on the total solid content excluding the solvent. The polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability and adhesion.

<Photopolymerization initiator>

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

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

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

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

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

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

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

&Lt; EMI ID =

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

&Lt; EMI ID =

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

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

As the halogenated hydrocarbon compound having a triazine skeleton, for example, see Wakabayashi et al., Bull. Chem. Soc. The compound described in GB-A-1388492, the compound described in JP-A-53-133428, the compound described in GB-A-3337024, the compound described in FC Schaefer et al. J. Org. Chem. ; 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds disclosed in JP-A-5-34920, A compound described in Japanese Patent Publication No. 4212976, particularly a compound described in Japanese Patent Laid-Open Publication No. 2013-077009, paragraph No. 0075, and the like.

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

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

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

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used. As the acylphosphine-based initiator, commercially available IRGACURE-819 and DAROCUR-TPO (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 the oxime compounds such as oxime derivatives suitably used as the photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3- 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan- - (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

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

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF) and TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) .

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

Preferably, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Of the cyclic oxime compounds, cyclic oxime compounds which are condensed in the carbazol dye described in JP-A-2010-32985 and JP-A-2010-185072 are particularly preferable from the viewpoint of high light absorbability and high sensitivity.

The compound described in Japanese Unexamined Patent Application Publication No. 2009-242469 having an unsaturated bond at a specific site of an oxime compound can also be suitably used because high sensitivity can be achieved by regenerating active radicals from polymerization inert radicals.

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

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

&Lt; EMI ID =

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

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

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

Specific examples (C-4) to (C-13) of the oxime compounds suitably used are shown below, but the present invention is not limited thereto.

&Lt; EMI ID =

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

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

Specifically, the molar extinction coefficient of the compound can be measured by using an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L .

When the photopolymerization initiator is contained in the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 30% , More preferably 1 mass% or more and 20 mass% or less. 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.

<Pigment>

The coloring composition of the present invention may further contain a colorant other than the above-mentioned colorant multimer. Concretely, it is preferable to contain a pigment.

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

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

As the organic pigment, for example,

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

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

C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 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, 7;

And the like.

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

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

C. I. Pigment Orange 36, 71,

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

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

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

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

C. I. Pigment Black 1, 7

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

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

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

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

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

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

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

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

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

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

In the present invention, dyes other than the above-mentioned colorant multimer and pigments other than those described above may be contained. 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 a pyrazole azo group, an anilino group, a triphenylmethane group, an anthraquinone group, a benzylidene group, an oxolane group, a pyrazolotriazoazo group, a pyridazo group, a sacynide, a phenothiazine group, And a pyrazole azo methane-based dye.

<Pigment dispersant>

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

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

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

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

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

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

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

DA-7301 "manufactured by Goosumoto Kasei Co., Ltd.," Disperbyk-101 "(polyamide amine phosphate) manufactured by BYK Chemie, 107 (trade name) manufactured by BYK Chemie, and a pigment dispersant available for use in the present invention (Carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161,162,163,164,165,166,170 (polymeric copolymer) "," BYK-P104, P105 EFKA 4047, 4050 to 4010 to 4165 (polyurethane resin), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester resin), " high molecular weight unsaturated polycarboxylic acid " Amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), azinophene azzepers PB821, PB822, PB880, PB881 Quot; Fluorene TG-710 (uretene oligomer) ", "Polyflur No. 50E, No. 300 (available from Kyoeisha Chemical Co., 873, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705 , DA-725 ", "Demol RN, N (naphthalene sulfonic acid-formaldehyde polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L- (Polyoxyethylene nonylphenyl ether), "acetamine 86 (stearylamine acetate) ", Nippon Lubrizol Co., Ltd." SOLSPERS 5000 28000, 32000, 38500 (graft polymer) ", Nikko Co., Ltd.), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by Chemicals Corporation, Hinoact T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd., and Shin- (week) , Organosiloxane polymer KP341, "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl Nonionic surfactants such as phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as "W004, W005, W017 & Based surfactant, EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450, manufactured by Morishita Sangyo Co., F38, L42, L44, L61, L64, F68, L72, L64, L64, L64, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 "and" Ionet (trade name) S-20 "and the like.

These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersing agent. The pigment dispersant may be used in combination with an alkali-soluble resin together with an end-modified polymer having an anchor portion on the surface of the pigment, a graft-type polymer, and a block-type polymer. Examples of the alkali-soluble resin include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain. Particularly, a (meth) acrylic acid copolymer is preferable. The N-substituted maleimide monomer copolymer 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. Specifically, an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.

In the case of containing the pigment dispersant in the coloring composition, the total content of the pigment dispersant is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and more preferably 10 parts by mass per 100 parts by mass of the pigment To 60 parts by mass is more preferable. The specific dispersion resin is preferably 50 mass% or more, more preferably 60 mass% or more, and most preferably 70 mass% or more, of the dispersant components contained in the coloring composition.

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

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

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

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

<(F) Alkali-soluble resin>

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

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

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

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

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

Further, in the case of introducing an acid group as a monomer component into a monomer capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

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

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic acid copolymer, and alkali-soluble phenol resin such as novolak resin, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydride added to a polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and another 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. In addition, these monomers copolymerizable with (meth) acrylic acid may be either one type alone or two or more types.

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

(108)

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)

(109)

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

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

Specific examples of the ether dimer include dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2' - [oxybis (Isopropyl) -2,2 '- [oxybis (methylene)] -2-propenoate, di (n-propyl) )] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (methylene)] bis- Di (tert-butyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (tert- Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) -2 Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di -Methoxyethyl) -2,2 ' - [ Bis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2 '- [oxybis - [oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 '- [oxy Bis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2,2 '- [oxybis ) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) Bis (2-hydroxyethyl) -2, 2 '- [oxybis (methylene)] bis-2-propenoate, diadamantyl- , Di (2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be either one kind or two or more kinds. The structure derived from the compound represented by the formula (ED) may be copolymerized with another monomer.

The alkali-soluble resin may contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).

In general formula (X)

(110)

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

In the formula (X), the number of carbon atoms of the alkylene group of R ² is preferably 2 to 3. The alkyl group of R ³ has 1 to 20 carbon atoms, more 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.

In order to improve the crosslinking efficiency of the coloring composition of the present invention, it is preferable to use an alkali-soluble resin having a polymerizable group. When such an alkali-soluble resin is used, the effect of the present invention tends to be further improved. Further, the light resistance and the heat resistance tend to be further improved. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include DYNAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), Viscot R-264, KS (All manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series, and Plaxcel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) . As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a Acrylic resin containing an unsaturated group obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule, a polymerizable double bond-containing acrylic resin obtained by a reaction of an acrylic resin, Acid pendant epoxy acrylate resin, a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, an isocyanate and a polymerizable group , A resin obtained by reacting a compound having an epoxy group-containing compound 207 and JP-A No. 2003-335814, a resin obtained by basic treatment of a resin having on its side chain an ester group having a leaving group such as a halogen atom or a sulfonate group on?

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

As the alkali-soluble resin, reference may be made to 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 It is preferable to use the binder resin as described in [0072]. The contents of which are incorporated herein by reference. More specifically, the following resins are preferable.

(111)

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

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

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

The composition of the present invention may contain only one 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.

<Other Ingredients>

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

<< Organic solvents >>

The coloring composition of the present invention may contain an organic solvent.

The organic 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, coating ability, and safety of an ultraviolet absorber, an alkali-soluble resin or a dispersant . In preparing the coloring composition of the present invention, it is preferable to include at least two kinds of organic solvents.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl acetate, methyl lactate, ethyl lactate, alkyloxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Ethoxyacetic acid ethyl, etc.), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and 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-oxypropionate Propyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) , Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- Examples of the organic solvent include methyl ethyl ketone, methyl ethyl ketone, ethyl methyl ketone, methyl ethyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, But are not limited to, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, , For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like, and aromatic hydrocarbons such as toluene and xylene.

From the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, and improvement of the shape of the coated surface, these organic solvents are also preferably mixed with two or more kinds. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- A mixed solution composed of two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate to be.

The content of the organic solvent in the coloring composition is preferably such that the total solid content concentration of the composition is 5% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, And particularly preferably from 10% by mass to 50% by mass.

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

<< Cross-linking agent >>

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

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

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

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

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

<< Polymerization inhibitor >>

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

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

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

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

<< Surfactant >>

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

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

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

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

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

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), 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 YUHO Co., Ltd.).

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

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

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

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

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

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

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

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

The composition of the present invention may contain 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.

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

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

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

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

&Lt; Preparation method of colored composition >

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

Further, at the time of 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 sequentially. 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 prepared as described above is preferably filtered and separated by using a filter having a pore diameter of 0.01 to 3.0 m, more preferably a pore diameter of about 0.05 to 0.5 m, have.

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

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

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

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

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

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

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

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

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

In the present invention, it is more preferable to manufacture by photolithography.

The details of these will be described below.

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

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

In the step of forming the coloring composition layer, a step of forming a coloring composition layer is formed on the support by applying the coloring composition of the present invention.

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

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

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

If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate. The undercoat layer may contain a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like. These components may be appropriately selected from components incorporated in the composition of the present invention .

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

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

&Lt; Step of forming pattern by photolithography method >

<< Process of Exposure >>

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

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

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

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

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

<< Development Process >>

Subsequently, by performing the alkali developing treatment, the coloring composition layer in the tailing portion in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured portion.

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

Examples of the alkaline agent to be used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide And organic alkaline compounds such as benzyl trimethyl ammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene. These alkaline compounds Is diluted with pure water to a concentration of 0.001 mass% to 10 mass%, preferably 0.01 mass% to 1 mass%, is preferably used as the developing solution.

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

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

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

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

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

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

In the case of forming a pattern by dry etching, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2013-64993, the contents of which are incorporated herein by reference.

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

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

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

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

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

The color filter of the present invention can be suitably used for a solid-state image pickup device such as a CCD and a CMOS, and is particularly suitable for a 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 the configuration includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.

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

It is also possible to use a configuration having the condenser (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 the condenser on the color filter.

<Image Display Device>

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

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

The color filter of the present invention may be used in a color TFT 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 above-mentioned usual required characteristics. In the color filter of the present invention, since a colorant multimer having excellent color is used, the COA type liquid crystal display (liquid crystal display) of high resolution and long-term durability is excellent in color purity and light transmittance, Device can be provided. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

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

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

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

When a color filter according to the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a conventional three-wavelength tube of a cold cathode tube. Further, a red LED, a green 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 exceeds the object thereof. Unless otherwise stated, "%" and "part" are based on mass.

&Lt; Synthesis Example 1 &

(112)

8.0 g of the monomer (a-1), 2.0 g of methacrylic acid, and 0.5 g of 2-cyano-2-propyldodecyltricyanocarbonate were dissolved in 20.0 g of cyclohexanone and heated to 80 DEG C in a nitrogen stream. Then, 0.1 g of 2,2'-azobis (methyl 2-methylpropionate) was added and the mixture was heated and stirred for 2 hours. Further, 0.1 g of 2,2'-azobis (methyl 2-methylpropionate) was added, and the mixture was heated for 2 hours and then heated at 90 ° C for 2 hours. Next, 1.0 g of glycidyl methacrylate and 0.010 g of tetrabutylammonium bromide were added, and the mixture was heated at 100 占 폚 for 10 hours. The reaction solution was added dropwise to a mixture of 100 mL of methanol and 100 mL of water, and the precipitated solid was filtered and dried to obtain 7.5 g of (A-1).

&Lt; Synthesis Examples 2 to 8 &

(A-2) to (A-8) were obtained in the same manner as in Synthesis Example 1 except that the monomer (a-1) was changed to (a-2) to (a-8).

(113)

&Lt; Synthesis Example 9 &

(A-9) was obtained in the same manner as in Synthesis Example 1, except that 2-cyano-2-propyldodecyltricyanocarbonate was changed to 2-cyano-2-propylbenzodithioate.

(114)

&Lt; Synthesis Example 10 &

(115)

8.0 g of the monomer (a-1), 2.0 g of methacrylic acid and 0.5 g of (b-1) were dissolved in 8.0 g of cyclohexanone and heated to 140 캜 under a nitrogen stream. To this, 0.1 g of benzoyl peroxide was added and the mixture was heated and stirred for 2 hours. An additional 0.1 g of benzoyl peroxide was added and heated for 2 hours. Next, 1.0 g of glycidyl methacrylate and 0.010 g of tetrabutylammonium bromide were added, and the mixture was heated at 100 占 폚 for 10 hours. The reaction solution was added dropwise to a mixture of 100 ml of methanol and 100 ml of water, and the precipitated solid was filtered and dried to obtain 8.5 g of (A-13).

&Lt; Synthesis Examples 11 and 12 >

(A-11) and (A-12) were obtained by carrying out the same operations except that the compound (b-1) of Synthesis Example 10 was changed to the following compounds (b-2) and (b-3), respectively.

&Lt; EMI ID =

(117)

&Lt; Synthesis Example 13 &

(118)

8.0 g of the monomer (a-2), 2.0 g of styrene carboxylic acid and 0.5 g of 2,2,6,6-tetramethylpiperidine-1-oxyl free radical were dissolved in 8.0 g of cyclohexanone, Lt; 0 &gt; C. To this, 0.1 g of benzoyl peroxide was added and the mixture was heated and stirred for 2 hours. An additional 0.1 g of benzoyl peroxide was added and heated for 2 hours. Next, 1.0 g of glycidyl methacrylate and 0.010 g of tetrabutylammonium bromide were added, and the mixture was heated at 100 占 폚 for 10 hours. The reaction solution was added dropwise to a mixture of 100 ml of methanol and 100 ml of water, and the precipitated solid was filtered and dried to obtain 8.5 g of (A-13).

Synthesis Example 14 Synthesis of block polymer

8.0 g of the monomer (a-1) and 0.5 g of 2-cyano-2-propyldodecyl trithiocarbonate were dissolved in 20.0 g of cyclohexanone and heated to 80 DEG C in a nitrogen stream. Then, 0.1 g of 2,2'-azobis (methyl 2-methylpropionate) was added and the mixture was heated and stirred for 2 hours. Further, 2.0 g of methacrylic acid and 0.1 g of 2,2'-azobis (methyl 2-methylpropionate) were added and heated for 2 hours and then heated at 90 ° C for 2 hours. Next, 1.0 g of glycidyl methacrylate was added, and the mixture was heated to 140 캜 and heated for 10 hours. The reaction solution was added dropwise to a mixture of 100 mL of methanol and 100 mL of water, and the precipitated solid was filtered and dried to obtain 7.5 g of (A-14).

&Lt; Synthesis Example 15 &

(A-15) was obtained in the same manner as in Synthesis Example 1, except that 2-cyano-2-propyldodecyltricyanocarbonate was changed to dodecylmercaptan.

[Table 1]

1. Preparation of resist solution

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

&Lt; Composition of resist solution for undercoat layer >

Solvent: Propylene glycol monomethyl ether acetate (PGMEA) 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

· Dipentaerythritol hexaacrylate 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 photopolymerization initiator of a trihalomethyltriazine type (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, the resist solution was coated 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 to obtain a silicon wafer substrate with an undercoat layer.

3. Preparation of coloring composition

3-1-1. Blue (Pigment Blue 15: 6) Preparation of pigment dispersion

Blue Pigment Dispersion 1 was prepared as follows.

, 5.0 parts of Disperbyk 111 as a pigment dispersant, and 82.0 parts of PGMEA were dispersed in a beads mill (zirconia beads 0.3 mm in diameter) in an amount of 13.0 parts CI Pigment Blue 15: 6 (blue pigment, average particle size 55 nm) The mixture was mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ by using a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bionics Co., Ltd.) equipped with a pressure reducing mechanism. This dispersion treatment was repeated ten times to obtain a blue pigment dispersion 1 (CI Pigment Blue 15: 6 dispersion, pigment concentration: 13%) used for the coloring composition of Example or Comparative Example.

The particle size of the obtained blue pigment dispersion was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (Nikkiso Co., Ltd.)) and found to be 24 nm.

3-1-2. Green (Pigment Green 36) Adjustment of Pigment Dispersion

(CI Pigment Green 36 dispersion, pigment concentration 13 (CI Pigment Green 36)) was obtained in the same manner as in Example 1 except that CI Pigment Blue 15: 6 of 3-1-1 was changed to CI Pigment Green 36 %).

3-2. Preparation of coloring composition

(1) Coloring composition

The following components were mixed, dispersed and dissolved to obtain each of the colored compositions of Examples and Comparative Examples.

· Cyclohexanone 1.133 part

Alkali-soluble resin (J1, J2 or J3 shown below in Table 2) 0.030 part

Sol Spurs 20000 (1% cyclohexane solution, manufactured by Nippon Lubrizol Corporation) 0.125 part

Photopolymerization initiator (the following compounds (I-1) to (I-8) 0.012 part

· Dye (compound described in the following table) 0.040 part as solid content

Pigment dispersion (pigment concentration 13.0%) containing the pigment shown in the following table 0.615 part

· Polymerizable compound (dipentaerythritol hexaacrylate, KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 0.070 part

Glycerol propoxylate (1% cyclohexane solution) 0.048 part

(119)

Alkali-soluble resin

(120)

4. Fabrication of Color Filter by Coloring Composition

&Lt; Pattern formation >

Each of the coloring compositions of the prepared examples and comparative examples was coated on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in the above 2 to form a colored composition layer (coating film). Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 0.6 탆.

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

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 a CD-2000 (FUJIFILM ELECTRONIC MATERIALS Ltd.) for 60 seconds at 23 占 폚 to form a colored pattern on a silicon wafer substrate.

The silicon wafer having the colored pattern formed thereon was fixed to the horizontal rotary table by a vacuum chucking method and the silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotary device, To perform a rinsing treatment, and thereafter spray-dried.

Thus, a monochromatic color filter having a coloring pattern formed by the coloring composition of Example or Comparative Example was produced.

Thereafter, the size of the colored pattern was measured using a measurement SEM "S-9260A" (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern size becomes 1.0 mu m was defined as the optimum exposure amount.

5. Performance evaluation

5-1. Light resistance

- Fabrication of monochromatic color filters and evaluation of light resistance -

Each of the colored curable compositions obtained above was coated on a glass substrate using a spin coater so that the film thickness after drying was 0.6 占 퐉 and prebaked at 100 占 폚 for 120 seconds to obtain a monochromatic color filter for light resistance evaluation.

The resulting monochromatic color filter for evaluating light fastness was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux · h). The color difference (? E * ab value) of the monochromatic color filter before and after the xenon lamp irradiation was measured and used as an index of light fastness. When the value of? E * ab is small, the light resistance is good.

5-2. Heat resistance

The glass substrate coated with the obtained coloring composition was placed on a hot plate at 200 캜 so as to be in contact with the substrate surface and heated for 1 hour and then subjected to color difference measurement with a color meter MCPD-1000 (manufactured by Otsuka Denshi Co., Ltd.) (? E * ab value) was measured and evaluated as an index for evaluating the fastness to heat (heat fastness). The value of? E * ab indicates that the smaller the value, the better the heat resistance. The value of? E * ab is a value obtained from the following color difference formula by the spatial colorimetric system of CIE 1976 (L *, a *, b *) (Japanese Society of Color Science, New Color Science Handbook .266).

ΔE * ab = {(ΔL * ) 2 + (Δa *) 2 + (Δb *) 2} 1/2

5-3. Application property

The coating properties at the time of application of each coloring composition were evaluated by the following methods. That is, each of the coloring compositions was coated with a spin coater so that the film thickness after drying was 0.6 탆, and observed with an optical microscope to evaluate coatability. The evaluation criteria are as follows.

-Evaluation standard-

A: No coating irregularity was confirmed at all.

B: Some coating irregularity was confirmed.

C: Many coating irregularities were confirmed.

5-4. Developability

The number of the incompletely developed portions was counted by observing 100 portions removed with a developing solution of a colored pattern using a cross-section SEM "S-4800" (manufactured by Hitachi High-Technologies Corporation). The smaller the number, the better the developability.

5-5. Solvent resistance

The colored curable compositions of the examples and comparative examples obtained above were applied to a glass wafer using a spin coater so as to have a thickness of 0.6 mu m after drying and heated for 300 seconds on a 200 DEG C hot plate.

Propylene glycol monomethyl ether acetate (PGMEA) was added dropwise to the color filter obtained above, left for 120 seconds, and rinsed with running water for 10 seconds.

The spectral fluctuation of the transmittance before and after dropping the various liquids was measured using MCPD-3000 (manufactured by Otsuka Denshi Co., Ltd.), and the color difference? Eab was measured. The lower the? Eab, the better the solvent resistance.

[Table 2]

As is apparent from the above table, when a color filter is produced by using a photoresist using the composition of the present invention, a composition excellent in light resistance, heat resistance, coating property and solvent resistance can be obtained. It was also excellent in developability. Particularly, it has been found that the dye having a nitroxide having a triisocyanate and a t-butyl group as a terminal group exhibits particularly excellent performance.

6. Pattern formation by dry etching

Preparation of coloring composition

The following components were mixed and dissolved to obtain the respective colored compositions of Examples 37 to 72 and Comparative Examples 3 to 4.

· Cyclohexanone 1.133 part

· Colorant oligomers (compounds listed in the following table) 0.040 part as solid content

The above-mentioned blue pigment dispersion (pigment concentration 13.0%) 0.615 part

The polymerizable compound (EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., 1,2-epoxy-4- (2-oxiranyl) cyclohexane-1-ene of 2,2-bis (hydroxymethyl) water)) 0.070 part

Glycerol propoxylate (1% cyclohexane solution) 0.048 part

6-1. Light resistance

- Fabrication of monochromatic color filters and evaluation of light resistance -

Each of the colored curable compositions obtained above was coated on a glass substrate using a spin coater so that the film thickness after drying was 0.6 占 퐉 and prebaked at 100 占 폚 for 120 seconds to obtain a monochromatic color filter for light resistance evaluation.

The resulting monochromatic color filter for evaluating light fastness was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux · h). The color difference (? E * ab value) of the monochromatic color filter before and after the xenon lamp irradiation was measured and used as an index of light fastness. When the value of? E * ab is small, the light resistance is good.

6-2. Heat resistance

The glass substrate coated with the obtained coloring composition was placed on a hot plate at 200 캜 so as to be in contact with the substrate surface and heated for 1 hour and then measured with a color meter MCPD-1000 (manufactured by OTSUKA DENKI CO., LTD.), (? E * ab value) was measured and used as an index for evaluating the fastness to heat, and evaluated according to the following criteria. The value of? E * ab indicates that the smaller the value, the better the heat resistance. The value of? E * ab is a value obtained from the following color difference formula by the spatial colorimetric system of CIE 1976 (L *, a *, b *) (Japanese Society of Color Science, New Color Science Handbook .266).

ΔE * ab = {(ΔL * ) 2 + (Δa *) 2 + (Δb *) 2} 1/2

6-3. Application property

The coating properties at the time of application of each coloring composition were evaluated by the following methods. That is, each of the coloring compositions was coated with a spin coater so that the film thickness after drying was 0.6 탆, and observed with an optical microscope to evaluate coatability. The evaluation criteria are as follows.

-Evaluation standard-

A: No coating irregularity was confirmed at all.

B: Some coating irregularity was confirmed.

C: Many coating irregularities were confirmed.

6-4. Solvent resistance

The colored curable compositions of the examples and comparative examples obtained above were applied to a glass wafer using a spin coater so as to have a thickness of 0.6 mu m after drying and heated for 300 seconds on a 200 DEG C hot plate.

N-methylpyrrolidone was added dropwise to the color filter obtained above, and then left for 120 seconds, followed by rinsing with running water for 10 seconds.

The spectral fluctuation of the transmittance before and after dropping the various liquids was measured using MCPD-3000 (manufactured by Otsuka Denshi Co., Ltd.), and the color difference? Eab was measured. The lower the? Eab, the better the solvent resistance.

[Table 3]

It was found that when the color filters were produced by the etching resist using the compositions of Examples 23 to 44, they were excellent in light resistance, heat resistance, coating ability and solvent resistance. On the other hand, the compositions of Comparative Examples 4 to 6 were inferior to those of Comparative Examples 4 to 6.

&Lt; Example 45 >

In the same manner as in Example 1 except that the polymerizable compound in Example 1 was changed to the same mass of A-DPH-12E (ethyleneoxy-modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) As a result, the same favorable results as in Example 1 can be obtained.

Claims (19)

A colorant composition having a dye structure and having a group represented by the general formula (I) or a group represented by the general formula (II) at the main chain terminal, and a polymerizable compound;
The compound of formula (I)
[Chemical Formula 1]

In the general formula (I), Z represents a hydrogen atom or a monovalent substituent; * Represents the bonding position with the main chain terminal;
In general formula (II)
(2)

In formula (II), A and B each independently represent a monovalent substituent; A and B may be connected to each other to form a ring; * Represents the bonding position with the main chain terminal. The method according to claim 1,
Further comprising a photopolymerization initiator. The method according to claim 1 or 2,
&Lt; / RTI &gt; further comprising a pigment. The method according to any one of claims 1 to 3,
Wherein a dispersion degree of the dye multimer is Mw / Mn of 1.0 to 1.8. The method according to any one of claims 1 to 4,
Further comprising an alkali-soluble resin. The method according to any one of claims 1 to 5,
Wherein the dye multimer is a random polymer of a polymerizable compound different from the polymerizable compound containing a dye. The method according to any one of claims 1 to 6,
Wherein the dye multimer comprises at least one of a dipyramethane dye, a triarylmethane dye, a xanthene dye, an azo dye, a cyanine dye and a squarylium dye. The method according to any one of claims 1 to 7,
Wherein at least one of the dye multimer is a styrene-based resin or a (meth) acrylic-based resin. The method according to any one of claims 1 to 8,
Z in the general formula (I) is selected from an amino group, an alkoxy group and an aryloxy group substituted with at least one of -SR ¹ , an aryl group, a heteroaryl group, an alkyl group and an aryl group, Wherein A and B are each independently an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms; R ¹ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a monovalent heterocyclic group having 3 to 30 total atoms of a carbon atom and a bivalent atom And A and B may be connected to each other to form a ring. The method of claim 9,
Wherein Z in Formula (I) is -SR ¹ or an aryl group, or A and B in Formula (II) are each independently a secondary or tertiary alkyl group having 1 to 30 carbon atoms, ; Provided that A and B may be bonded to each other to form a ring. The method according to any one of claims 1 to 10,
Coloring composition for a color filter. A step of applying a coloring composition according to any one of claims 1 to 11 on a support to form a coloring composition layer; a step of exposing the coloring composition layer to a pattern shape; To form a pattern. A manufacturing method of a color filter, comprising the pattern forming method according to claim 12. A color filter produced by using the coloring composition according to any one of claims 1 to 11 or the color filter according to claim 13. A solid-state image pickup device having the color filter according to claim 14. An image display apparatus having the color filter according to claim 14. A method for producing a coloring composition, which comprises living-radical-polymerizing a polymerizable compound having a dye structure and then blending a polymerizable compound. 18. The method of claim 17,
In the presence of at least one of a compound represented by the general formula (Ia), a compound represented by the general formula (IIa) and a radical represented by the general formula (IIb), a polymerizable compound having a pigment structure and another polymerizable compound are subjected to radical polymerization A method of making a coloring composition, comprising:
(Ia)
(3)

In the general formula (Ia), Z is synonymous with the general formula (I); C represents a monovalent organic group;
The compound of formula (IIa)
[Chemical Formula 4]

In the general formula (IIa), Z corresponds to the general formula (II); D represents a monovalent organic group;
(IIb)
[Chemical Formula 5]

In the general formula (IIb), A and B are synonymous with the general formula (II). The method according to claim 17 or 18,
Wherein the coloring composition is the coloring composition according to any one of claims 1 to 11.