JPWO2016031442A1 - COLORING COMPOSITION, COLOR FILTER, PATTERN FORMING METHOD, COLOR FILTER MANUFACTURING METHOD, SOLID-STATE IMAGING DEVICE, IMAGE DISPLAY DEVICE, AND DYE MULTIMER MANUFACTURING METHOD - Google Patents

Abstract

A coloring composition contains the pigment | dye multimer represented by General formula (1), and a polymeric compound. In general formula (1), P represents an n-valent linking group, Q represents a polymer chain containing a repeating unit having a dye structure, and an average value of the number of repeating units of n Q having a dye structure is 2 or more, and n represents an integer of 3 to 10. P- (Q) n (1)

Description

  The present invention relates to a colored composition. In particular, the present invention relates to a coloring composition suitable for a color filter used in a solid-state imaging device, an image display device and the like. The present invention also relates to a color filter, a solid-state imaging device, and an image display device using the coloring composition. The present invention also relates to a pattern forming method using a colored composition, a color filter manufacturing method, and a dye multimer manufacturing method.

  In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, the demand for solid-state imaging devices such as charge coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for higher sensitivity and miniaturization. Such a color filter normally has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and plays a role of separating transmitted light into the three primary colors.

  The colorant used in the color filter is required to have the following properties in common. That is, it is required to have a light absorption characteristic that is favorable for color reproducibility and to have good light resistance.

  On the other hand, Patent Document 1 discloses a pigment dispersant having 2 to 9 sites having adsorption ability for a pigment in one molecule. As the site having the ability to adsorb to pigment, organic dye structure, heterocyclic structure, acidic group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, hydrocarbon having 4 or more carbon atoms Groups, alkoxysilyl groups, epoxy groups, isocyanate groups, hydroxyl groups, ionic functional groups and the like.

JP 2008-222950 A

In the coloring composition used for a color filter etc., further improvement of light resistance, a color transfer property, and flatness is calculated | required.
Patent Document 1 is an invention related to a pigment dispersant. Patent Document 1 describes that an organic dye structure may be used as a site having the ability to adsorb pigments. However, since the pigment dispersant preferably has no color, it has an ability to adsorb pigments. It is necessary to select a structure having a low absorbance as the site to have. In addition, Patent Document 1 does not include a motivation to use a pigment dispersant as a colorant.

  This invention is made | formed in view of this condition, and it aims at providing the coloring composition excellent in light resistance, a color transfer property, and flatness. It is another object of the present invention to provide a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, an image display device, and a dye multimer manufacturing method.

As a result of detailed studies, the present inventors have found that light resistance, color transfer and flatness are obtained by using a dye multimer in which n polymer chains including a repeating unit having a dye structure are bonded to an n-valent linking group. The inventors have found that a colored composition excellent in the above can be obtained, and have completed the present invention. Therefore, the present invention provides the following.
<1> A colored composition comprising a dye multimer represented by the general formula (1) and a polymerizable compound;
P- (Q) _n (1)
In general formula (1), P represents an n-valent linking group,
Q represents a polymer chain containing a repeating unit having a dye structure;
The average value of the number of repeating units of n Q having a dye structure is 2 or more,
n represents an integer of 3 to 10.
<2> The coloring composition according to <1>, wherein the dye multimer represented by the general formula (1) is represented by the general formula (2);

In General Formula (2), A ¹ represents an n-valent linking group,
B ¹ represents a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—,
R represents a hydrogen atom, an alkyl group or an aryl group,
C ¹ represents a single bond or a divalent linking group,
S represents a sulfur atom,
Q represents a polymer chain containing a repeating unit having a dye structure;
The average value of the number of repeating units of n Q having a dye structure is 2 or more,
n represents an integer of 3 to 10.
<3> A ¹ is a group composed of one or a combination of two or more selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain. The coloring composition as described in 2>.
<4> The coloring composition according to any one of <1> to <3>, wherein the dye multimer has a specific absorbance represented by the following formula (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm of 5 or more. object;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml.
<5> The colored composition according to any one of <1> to <4>, containing 1 to 50% by mass of a dye multimer based on the total solid content of the colored composition.
<6> The dye multimer is obtained by radical polymerization of a compound represented by the general formula (3) and a compound having a dye structure and a radical polymerizable group, according to <1> to <5>. The coloring composition in any one.
P ⁰ − (SH) _n (3)
In general formula (3), P ⁰ represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.
<7> The colored composition according to any one of <1> to <6>, further including a dye other than the dye multimer.
<8> The colored composition according to any one of <1> to <7>, further including a photopolymerization initiator.
<9> Q has a dye structure derived from a dye selected from a triarylmethane dye, a xanthene dye, an anthraquinone dye, a cyanine dye, a squarylium dye, a quinophthalone dye, a phthalocyanine dye, a subphthalocyanine dye, an azo dye, and a dipyrromethene dye. The coloring composition in any one of <1>-<8>.
<10> The colored composition according to any one of <1> to <9>, wherein Q has one or more selected from a repeating unit having an acid group and a repeating unit having a polymerizable group.
<11> Q is a coloring composition according to any one of <1> to <10>, wherein Q is one selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins. object.
<12> A color filter using the colored composition according to any one of <1> to <11>.
<13> A step of applying the colored composition according to any one of <1> to <11> on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, Forming a colored pattern by developing and removing unexposed portions of the colored composition layer exposed in a pattern.
<14> A step of applying the colored composition according to any one of <1> to <11> on a support to form a colored composition layer and curing to form a colored layer; A step of forming a photoresist layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask to form a colored pattern. A pattern forming method.
<15> A method for producing a color filter, comprising the pattern forming method according to <13> or <14>.
<16> A solid-state imaging device having the color filter according to <12> or the color filter obtained by the method for producing a color filter according to <15>.
<17> An image display device having the color filter according to <12> or the color filter obtained by the method for producing a color filter according to <15>.
<18> A method for producing a dye multimer, comprising radically polymerizing a compound represented by the general formula (3) and a compound having a dye structure and a radical polymerizable group.
P ⁰ − (SH) _n (3)
In general formula (3), P ⁰ represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the coloring composition excellent in light resistance, color transfer property, and flatness. In addition, it is possible to provide a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, an image display device, and a dye multimer manufacturing method.

Hereinafter, the contents of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, light means actinic rays or radiation. “Actinic light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
In this specification, unless otherwise specified, “exposure” is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. Include drawing in exposure.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm) can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

<Coloring composition>
The coloring composition of this invention contains the pigment | dye multimer shown by General formula (1) mentioned later, and a polymeric compound.
By setting it as the said structure, the coloring composition excellent in light resistance, color transfer property, and flatness can be provided.
The reason why such an effect is obtained is not yet clear, but the dye multimer represented by the general formula (1) described later is a polymer chain containing a repeating unit having a dye structure in an n-valent linking group. It is considered that the entanglement of polymer chains having a dye structure was less than that of a linear dye multimer. For this reason, it is considered that the dye multimer hardly aggregated and a film having excellent flatness could be obtained. Further, since the dye structure is incorporated in the polymer chain, it is considered that the dye is difficult to diffuse and excellent in color transfer. In addition, it is considered that the dye multimer improves adsorbability with other molecules such as pigments, and facilitates energy transfer between molecules, so that light resistance is also excellent.
In addition, for example, in the case of pattern formation by a photolithography method, entanglement of polymer chains having a dye structure can be reduced, so that the developer can be satisfactorily penetrated, the development speed is high, and development residues are hardly generated. You can also. Hereinafter, the present invention will be described in detail.

<< Dye Multimer Shown by General Formula (1) >>
The colored composition of the present invention contains a dye multimer represented by the following general formula (1) (hereinafter sometimes simply referred to as “dye multimer (A)”).

  The dye multimer (A) preferably has a maximum absorption wavelength in the range of 400 nm to 800 nm. The dye multimer (A) functions as, for example, a colorant in the colored composition of the present invention.

P- (Q) _n (1)
In general formula (1), P represents an n-valent linking group,
Q represents a polymer chain containing a repeating unit having a dye structure;
The average value of the number of repeating units of n Q having a dye structure is 2 or more,
n represents an integer of 3 to 10.

<<< Linking group P >>>
In general formula (1), P represents an n-valent linking group.
n-valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.
The n-valent linking group represented by P includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and Groups consisting of 0 to 10 sulfur atoms are preferred. More preferably, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 atoms. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.
The n-valent linking group represented by P is preferably a linking group derived from a polyhydric alcohol.

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

In General Formula (2), A ¹ represents an n-valent linking group,
B ¹ represents a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—,
R represents a hydrogen atom, an alkyl group or an aryl group,
C ¹ represents a single bond or a divalent linking group,
S represents a sulfur atom,
Q represents a polymer chain containing a repeating unit having a dye structure;
The average value of the number of repeating units of n Q having a dye structure is 2 or more,
n represents an integer of 3 to 10.

The structure of the following formula (2a) excluding Q in the general formula (2) corresponds to the linking group P in the general formula (1). * Represents a bonding position with Q.

In the general formula (2), A ¹ represents an n-valent linking group.
The n-valent linking group is preferably a group consisting of one or a combination of two or more selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain.
Examples of the aliphatic hydrocarbon group include an alkylene group and an alkenylene group. 1-60 are preferable, for example, and, as for carbon number of an alkylene group, 1-30 are more preferable. 1-60 are preferable, for example, and, as for carbon number of an alkenylene group, 1-30 are more preferable.
Examples of the aliphatic hydrocarbon group having an oxygen atom in the main chain include groups represented ^by- (OR ^x1 ) _m- ^and- (R ^x1 O) _m- . The aliphatic hydrocarbon group having an oxygen atom in the main chain may be linear, branched or cyclic. The main chain refers to a skeleton portion of a linking group and does not include a substituent.
R ^x1 represents an alkylene group or an alkenylene group. m represents an integer of 1 or more. When m is 2 or more, m R ^{x1 s} may be the same or different.
1-20 are preferable, as for carbon number of the alkylene group which ^Rx1 represents, 1-10 are more preferable, and 1-5 are still more preferable. The alkylene group may be linear, branched or cyclic.
The number of carbon atoms of the alkenylene group R ^x1 represents preferably 2 to 20, more preferably 2 to 10, 2 to 5 are more preferred. The alkenylene group may be linear, branched or cyclic.
The aromatic ring group may be monocyclic or polycyclic. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a chrysene ring, a triphenylene ring, a fluorene ring, and a biphenyl ring, and a benzene ring is preferable.
The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be monocyclic or polycyclic. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. A nitrogen atom is preferred. The number of heteroatoms is preferably 1 to 3. As the heterocyclic ring, for example, cyanuric ring, triazine ring, oxane ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene A ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring, and a cyanuric ring, a triazine ring, and an oxane ring are preferable.
The n-valent linking group represented by A ¹ includes a hydrocarbon group that may have an oxygen atom in the main chain, an aromatic ring group, a heterocyclic group, and a hydrocarbon group that may have an oxygen atom in the main chain; Preferred examples include a combination with an aromatic ring group and a combination of a hydrocarbon group that may have an oxygen atom in the main chain and a heterocyclic group.
A ¹ is an aromatic ring group, a heterocyclic group, a combination of a hydrocarbon group that may have an oxygen atom in the main chain and an aromatic ring group, or a carbon that may have an oxygen atom in the main chain Examples of the linking group P (the above formula (2a)) in the case of a combination of a hydrogen group and a heterocyclic group include the following.

In the formula, X represents a hydrocarbon group which may have an oxygen atom in the main chain,
B ¹ represents a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—,
R represents a hydrogen atom, an alkyl group or an aryl group,
C ¹ represents a single bond or a divalent linking group,
S represents a sulfur atom,
n represents an integer of 3 or more,
* Represents a bonding position with Q.

In the general formula (2), B ¹ represents a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—. A single bond, —O—, —CO—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR— is preferable.
R represents a hydrogen atom, an alkyl group or an aryl group.
1-30 are preferable and, as for carbon number of the alkyl group which R represents, 1-10 are more preferable. The alkyl group may be linear, branched or cyclic.
6-30 are preferable and, as for carbon number of the aryl group which R represents, 6-12 are more preferable.
R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

In the general formula (2), C ¹ represents a single bond or a divalent linking group.
The divalent linking group is preferably an alkylene group, an arylene group or an oxyalkylene group, more preferably an alkylene group or an oxyalkylene group.
1-30 are preferable and, as for carbon number of an alkylene group and an oxyalkylene group, 1-10 are more preferable. The alkyl group and oxyalkylene group may be linear, branched or cyclic.
6-30 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable.

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

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

<<< Polymer chain Q >>>
The polymer chain represented by Q represents a polymer chain including a repeating unit having a dye structure, and the average value of the number of repeating units of n Q having a dye structure is 2 or more. For n Q contained in the general formula (1) or (2), two or more repeating units having a dye structure are contained per Q1. The dye multimer represented by the general formula (1) or (2) includes 2n or more repeating units having a dye structure. The n Qs may be the same or different.
The polymer chain represented by Q preferably has an average value of 2 to 20 repeating units having a dye structure, more preferably 2 to 15 and even more preferably 2 to 10.
The average value of the number of repeating units having a dye structure can be determined by NMR (nuclear magnetic resonance). Specifically, for example, the number of repeating units in the general formula (1) is determined from the peak area ratio between the n-valent linking group represented by P and the repeating units of the polymer chain Q. Next, the number of repeating units in the polymer chain Q can be calculated by dividing the value by n.
The weight average molecular weight of the polymer chain Q is preferably 1,000 to 100,000, more preferably 1000 to 30,000, and particularly preferably 1,000 to 10,000.

The dye structure of each repeating unit may be the same dye structure or the same skeleton, but may be a different dye structure such as a substituent or a central metal, or a dye structure having a different skeleton. May be.
When the dye structure has a cation and an anion, the cation and the anion may be in the same molecule of the dye structure that the polymer chain Q has, or may be outside the molecule of the dye structure. In addition, having a cation and an anion in the same molecule | numerator of pigment | dye structure means the case where the cation and an anion are couple | bonded through a covalent bond. Also, having an anion outside the molecule of the dye structure means that the cation and the anion are not bonded via a covalent bond but are present as separate compounds. Hereinafter, an anion outside the molecule of the dye structure is also referred to as a counter anion.

The polymer chain represented by Q is not particularly defined as long as it contains a dye structure, but is a kind selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins. Preferably there is.
The (meth) acrylic resin means a resin containing a (meth) acrylic resin as a main component. Containing a (meth) acrylic resin as a main component preferably includes (meth) acrylic resin in an amount of 50% by mass or more, more preferably 60% by mass or more in the (meth) acrylic resin. It is particularly preferable to contain at least mass%.
The styrene resin means a resin containing a styrene resin as a main component. Containing styrene resin as a main component means that the styrene resin preferably contains 50% by mass or more of styrene resin, more preferably 60% by mass or more, and particularly preferably 70% by mass or more. .
The (meth) acrylic / styrene resin means a resin containing a (meth) acrylic resin and a styrene resin as main components. When the (meth) acrylic resin and the styrene resin are contained as main components, the (meth) acrylic / styrene resin preferably contains a total of 50% by mass of the (meth) acrylic resin and the styrene resin. % Or more is more preferable, and 70% by mass or more is particularly preferable.
Hereinafter, the polymer chain Q will be described in detail.

<<<<< skeleton structure of repeating unit having a dye structure >>>>
The skeleton structure of the repeating unit having a dye structure is not particularly defined, but is represented by general formulas (A), (B), and general It is preferable that at least one of the structural units represented by the formula (C) is a skeleton, or a dye multimer represented by the general formula (D) is preferable. The description of paragraph numbers 0276 to 0304 of JP2013-28764 is incorporated in the present specification.
In this invention, it is preferable to have a repeating unit represented by the following general formula (a1-1).
The total number of repeating units having a dye structure in all repeating units constituting the polymer chain Q is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and more preferably 20 to 40 mol%. Further preferred.

In general formula (a1-1), Q ¹ represents a trivalent linking group, L ¹ represents a single bond or a divalent linking group, D ¹ represents a dye structure, and “*” represents a main chain. Represents a bond with

In general formula (a1-1), Q ¹ represents a trivalent linking group. Q ¹ is a linking group formed by polymerization and refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. In addition, the site | part represented by two "*" becomes a repeating unit.
Q ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but is particularly preferably a linking group represented by the following (XX-1) to (XX-24), (XX- (1) and a (meth) acrylic linking chain represented by (XX-2), a styrene linking chain represented by (XX-10) to (XX-17), (XX-18) and (XX-19) ), And a vinyl-based linking chain represented by (XX-24), (meth) acrylic linking chains represented by (XX-1) and (XX-2), XX-10) to (XX-17) are more preferably selected from styrenic linking chains represented by (XX-24) and vinyl linking chains represented by (XX-24), and (XX-1) and (XX- (Meth) acrylic linking chain represented by 2) and (XX-11) Styrene linking chain represented is more preferable.
In (XX-1) to (XX-24), it represents that L ¹ is linked at the site indicated by *.
Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

In general formula (a1-1), L < ¹ > represents a single bond or a bivalent coupling group each independently.
Examples of the divalent linking group include substituted or unsubstituted alkylene groups having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted groups having 6 to 30 carbon atoms. A substituted arylene group (for example, a phenylene group, a naphthylene group, etc.), a substituted or unsubstituted heterocyclic group, —CH═CH—, —O—, —S—, —C (═O) —, —CO ₂ —. , —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linking group formed by linking two or more thereof. In addition, L ¹ preferably includes an anion. L ¹ is preferably a single bond or an alkylene group, and 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 heteroaryl group.
D ¹ represents a dye structure derived from a dye compound described later.

<<<<< Dye Structure >>>>
There is no restriction | limiting in particular as a pigment | dye structure, The various thing containing a well-known pigment | dye structure is applicable.
For specific pigment compounds that can form pigment structures, see "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dye Handbook" (Okawara et al.) Ed., Kodansha, 1986).
For example, quinone dye (benzoquinone dye, naphthoquinone dye, anthraquinone dye, anthrapyridone dye, etc.), carbonium dye (diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, etc.), quinoneimine dye (oxazine dye, thiazine dye, etc.) , Azine dye, polymethine dye (oxonol dye, merocyanine dye, arylidene dye, styryl dye, cyanine dye, squarylium dye, croconium dye, etc.), quinophthalone dye, phthalocyanine dye, subphthalocyanine dye, perinone dye, indigo dye, thioindigo dye, quinoline And dye structures derived from dyes selected from dyes, nitro dyes, nitroso dyes, dipyrromethene dyes, azo dyes and their metal complex dyes. That.
Among these dye structures, triarylmethane dyes, xanthene dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, azo dyes, and dipyrromethene dyes from the viewpoint of color separation and light resistance. The dye structure selected is preferable, and the dye structure selected from triarylmethane dye, xanthene dye, anthraquinone dye, squarylium dye, quinophthalone dye, phthalocyanine dye, subphthalocyanine dye, azo dye and dipyrromethene dye is more preferable, triarylmethane dye, Xanthene dyes are more preferred. The dye structure contained in the polymer chain represented by Q may be only one type or two or more types.
Hereinafter, the dye structure preferably used in the present invention will be described in detail.

<<<<<<< Triarylmethane Dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a triarylmethane dye (triarylmethane compound). Examples of the triarylmethane dye include a compound represented by the following formula (TP). A triarylmethane compound is a general term for compounds having a dye moiety containing a triarylmethane skeleton in the molecule.

Formula (TP)

In the formula (TP), Rtp ^{1 to} Rtp ⁴ each independently represents a hydrogen atom, an alkyl group, or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent a hydrogen atom, an alkyl group or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent. a, b, and c represent an integer of 0-4. When a, b and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be linked to each other to form a ring. X ⁻ represents an anion structure. When X ⁻ is not present, at least one of Rtp ^{1 to} Rtp ⁷ contains an anion.

Rtp ^{1 to} Rtp ⁶ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp ⁵ is preferably a hydrogen atom or NRtp ⁹ Rtp ¹⁰ , particularly preferably NRtp ⁹ Rtp ¹⁰ . Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. As the substituent represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ , the substituents mentioned in the section of Substituent Group A described later can be used, and in particular, a linear or branched alkyl group having 1 to 5 carbon atoms, A C1-C5 alkenyl group, a C6-C15 aryl group, a carboxyl group, or a sulfo group is preferable, a C1-C5 linear or branched alkyl group, a C1-C5 alkenyl group, phenyl A group or a carboxyl group is more preferable. In particular, Rtp ⁶ and Rtp ⁸ are preferably an alkyl group having 1 to 5 carbon atoms, and Rtp ⁷ is preferably an alkenyl group (particularly a phenyl group in which two adjacent alkenyl groups are linked), a phenyl group or a carboxyl group. .
a, b or c each independently represents an integer of 0 to 4; In particular, a and b are each preferably 0 or 1, and c is preferably an integer of 0 to 2.

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

In General Formula (P), L represents a single bond or a divalent linking group, and X ¹ represents —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , or a structure represented by the following General Formula (A1). It is selected from at least one selected from a group containing and a group containing a structure represented by the following formula (A2)
General formula (A1)

In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.
General formula (A2)

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

In general formula (P), L represents a single bond or a divalent linking group. The divalent linking group preferably represents a group consisting of —NR ¹⁰ —, —O—, —SO ₂ —, a fluorine-substituted alkylene group, a fluorine-substituted phenylene group, or a combination thereof. In particular, a group consisting of a combination of —NR ¹⁰ —, —SO ₂ — and a fluorine-substituted alkylene group, a group consisting of a combination of —O— and a fluorine-substituted phenylene group, or —NR ¹⁰ — and —SO ₂ — A group consisting of a combination with a fluorine-substituted phenylene group is preferred.
In —NR ¹⁰ —, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably a hydrogen atom.
1-10 are preferable, as for carbon number of a fluorine-substituted alkylene group, 1-6 are more preferable, and 1-3 are more preferable. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of the fluorine-substituted alkylene group include a difluoromethylene group, a tetrafluoroethylene group, and a hexafluoropropylene group.
6-20 are preferable, as for carbon number of a fluorine substituted phenylene group, 6-14 are more preferable, and 6-10 are more preferable. Specific examples of the fluorine-substituted phenylene group include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.

In General Formula (P), X ¹ is an anion, including —SO ₃ ⁻ , —COO ⁻ , a group including a structure represented by General Formula (A1), and a structure represented by General Formula (A2). It is preferably selected from at least one selected from the group.
The group including the structure represented by the general formula (A1) preferably has a fluorine-substituted alkyl group at one terminal of R ¹ and R ² in the general formula (A1) described above, and R ¹ and R ² More preferably, one of these is directly bonded to a fluorine-substituted alkyl group. 1-10 are preferable, as for carbon number of a fluorine-substitution alkyl group, 1-6 are more preferable, 1-3 are more preferable, 1 or 2 is further more preferable, and 1 is especially preferable. These alkyl groups are more preferably perfluoroalkyl groups. As a specific example of the fluorine-substituted alkyl group, a trifluoromethyl group is preferable.
Group containing a structure represented by formula (A2), in the above-mentioned general formula (A2), at least either end of R ³ to R ^5, preferably has a fluorine-substituted alkyl group, R ³ ~ More preferably, at least two of R ⁵ are directly bonded to a fluorine-substituted alkyl group. In particular, at least two ends of R ³ to R ^5, preferably has a fluorine-substituted alkyl group, it is more preferably bonded to at least two of direct fluorine-substituted alkyl group of R ³ to R ^5. A fluorine-substituted alkyl group is synonymous with what was demonstrated by group containing the structure represented by general formula (A1), and its preferable range is also the same.

<<<<<< Xanthene Dye >>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a xanthene dye (xanthene compound). Examples of the xanthene dye include xanthene compounds represented by the following formula (J).

In formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, m Represents an integer of 0 to 5. X ⁻ represents a counter anion. When X ⁻ is not present, at least one of R ^{81 to} R ⁸⁵ contains an anion.

The substituents that can be taken by R ^{81 to} R ⁸⁵ in the formula (J) are the same as the substituents mentioned in the section of the substituent group A described later.
R ⁸¹ and R ^{82 in} formula (J), R ⁸³ and R ⁸⁴ , and R ^{85 in} the case where m is 2 or more are each independently bonded to each other to form a 5-membered, 6-membered or 7-membered saturated ring. Or a 5-membered, 6-membered or 7-membered unsaturated ring. 5-membered to be formed, ring 6- or 7 members, in the case of further substitutable groups may be substituted with substituents described in R ⁸¹ to R ^85, 2 or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
In the above formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ^{85 in} the case where m is 2 or more are each independently bonded to each other, and have no substituent. 5-membered and 7-membered saturated ring or 5-membered, 6-membered and 7-membered unsaturated ring, when forming 5-membered, 7-membered saturated ring or 5-membered, 6-membered and 7-membered Examples of the unsaturated ring include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring and pyridine ring. , A pyrazine ring and a pyridazine ring, preferably a benzene ring and a pyridine ring.
Examples of the anion include those described above.

In particular, R ⁸² and R ⁸³ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R ⁸¹ and R ⁸⁴ are preferably 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 sulfonamide group, a carboxyl group or an amide group, and a sulfo group, a sulfonamide group, a carboxyl group, More preferred is an amide group. R ⁸⁵ is preferably bonded to the adjacent part of carbon linked to the xanthene ring. The substituent that the phenyl group of R ⁸¹ and R ⁸⁴ has is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.

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

When X ⁻ represents an anion, the description in the case where the counter anion described later is a different molecule can be referred to.
In addition, when X ⁻ does not exist and at least one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ contains an anion, the description of the case where the counter anion is in the same structural unit can be referred to.

In addition, since the cation is delocalized in the dye structure, for example, as shown below, the cation is present on a nitrogen atom or a carbon atom of the xanthene ring.

<<<<<<< Anthraquinone dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from an anthraquinone dye. As the anthraquinone dye (anthraquinone compound), compounds represented by the following general formulas (AQ-1) to (AQ-3) are preferable. An anthraquinone compound is a general term for compounds having a dye moiety containing an anthraquinone skeleton in the molecule.

In General Formula (AQ-1), A and B each independently represent an amino group, a hydroxyl group, an alkoxy group, or a hydrogen atom. Xqa represents ORqa ¹ or NRqa ² Rqa ^3. Rqa ^{1 to} Rqa ³ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq ₁ to Rq ₄ represents a substituent. The substituents that Rq _{1 to} Rq ₄ can take are the same as the substituents mentioned in the section of Substituent group A described later. Ra and Rb each independently represents a hydrogen atom, an alkyl group or an aryl group.

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

In general formula (AQ-3), E and F are synonymous with A and B in general formula (AQ-1). Xqc represents ORqc ¹ or NRqc ² Rqc ^3. Rqc ¹ ~Rqc ³ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq ₉ to Rq ₁₂ is formula synonymous with _{(AQ-1) Rq 1 ~Rq} 4 in. Rd has the same meaning as Ra or Rb in formula (AQ-1).
As preferable ranges of the general formulas (AQ-1), (AQ-2), and (AQ-3), for example, paragraphs 0045 to 0047 of JP-A-2013-29760 can be referred to, and the contents thereof are described in this application. Incorporated in the description.

  As the anthraquinone dye, for example, paragraphs 0049 to 0050 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

<<<<<<< cyanine dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a cyanine dye (cyanine compound). As the cyanine dye, a compound represented by the following general formula (PM) (cyanine compound) is preferable. In the present invention, the cyanine compound is a general term for compounds having a dye moiety containing a cyanine skeleton in the molecule.

In general formula (PM), ring Z1 and ring Z2 each independently represent a heterocyclic ring which may have a substituent. l represents an integer of 0 or more and 3 or less. X ⁻ represents an anion.
As a preferable range of the general formula (PM), for example, paragraphs 0077 to 0084 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. In the specific examples of the cyanine dyes described in paragraphs 0077 to 0084 of JP 2013-29760 A, any hydrogen atom in the cyanine dye structure is bonded to R ^{2 of the} general formula (1).

<<<<<<< Squarylium dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from squarylium dye (squarylium compound). As a squarylium pigment | dye, the compound (squarylium compound) represented by the following general formula (K) is preferable. In the present invention, the squarylium compound is a general term for compounds having a dye moiety containing a squarylium skeleton in the molecule.

In general formula (K), A and B each independently represent an aryl group or a heterocyclic group. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples thereof include pyroyl, imidazoyl, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, furyl, thiadiazoyl and the like.
As a preferable range of the general formula (K), for example, paragraphs 0088 to 0106 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the squarylium pigment, paragraph 0105 of JP 2013-29760 A can be referred to.

<<<<<<< Quinophthalone Dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a quinophthalone dye (quinophthalone compound). As the quinophthalone dye, a compound (quinophthalone compound) represented by the following general formula (QP) is preferable. In the present invention, the quinophthalone compound is a general term for compounds having a dye moiety containing a quinophthalone skeleton in the molecule.

In general formula (QP), Rqp _{1 to} Rqp ₆ each independently represents a hydrogen atom or a substituent. When at least two of Rqp _{1 to} Rqp ₆ are adjacent to each other, they may be bonded to each other to form a ring, and the formed ring may further have a substituent.
As a preferable range of the general formula (QP), for example, paragraphs 0110 to 0114 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the quinophthalone dye, the description in paragraph 0113 of JP2013-29760A can be referred to, for example.

<<<<<<< phthalocyanine dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a phthalocyanine dye (phthalocyanine compound). As the phthalocyanine dye, those having a partial structure derived from a compound represented by the following general formula (F) (phthalocyanine compound) are preferable. In the present invention, the phthalocyanine compound is a general term for compounds having a dye moiety containing a phthalocyanine skeleton in the molecule.

In the general formula (F), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently composed of an atom selected from a hydrogen atom, a carbon atom, and a nitrogen atom. Represents a group of atoms necessary to form a 6-membered ring.
As a preferable range of the general formula (F), for example, paragraphs 0118 to 0124 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the phthalocyanine dye, for example, paragraph 0123 of JP2013-29760A can be referred to.

<<<<<<< Subphthalocyanine Dye >>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a subphthalocyanine dye (subphthalocyanine compound). As the subphthalocyanine dye, a compound represented by the following general formula (SP) (subphthalocyanine compound) is preferable. In the present invention, the term “subphthalocyanine compound” is a general term for compounds having a dye moiety containing a subphthalocyanine skeleton in the molecule.

In the general formula (SP), Z ^{1 to} Z ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, or a thioether group. X represents an anion.
As a preferable range of the general formula (SP), for example, paragraphs 0128 to 0133 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As specific examples of the subphthalocyanine dye, reference can be made to, for example, the description in paragraph 0132 of JP2013-29760A.

<<<<<<< Azo dye >>>>>>
A preferred embodiment of the dye structure in the present invention has a partial structure derived from an azo dye (azo compound). In the present invention, the azo compound is a general term for compounds having a dye moiety containing an N = N group in the molecule. As the azo dye, a known azo dye (for example, substituted azobenzene) can be appropriately selected and applied. For example, as the azo dye, the description in paragraphs 0084 to 0134 of JP2013-41097A and the description of paragraphs 0029 to 0136 in JP2011-162760A can be referred to, and the contents thereof are incorporated in the present specification. .

<<<<<<< dipyrromethene dye >>>>>>
One of the aspects of the dye structure according to the present invention has a partial structure derived from a dipyrromethene dye. As the dipyrromethene dye, a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound are preferable. For example, as a dipyrromethene dye, description of paragraphs 0033 to 0136 of JP 2011-95732 A can be referred to, and the contents thereof are incorporated in the present specification.

In the dye structure, a hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A.
(Substituent group A)
Examples of the substituent that the dye structure may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). A chain, branched chain, or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl group (preferably t-butyl group), pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, Cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-butene- 1-yl), an alkynyl group (preferably having 2-20 carbon atoms, more preferably 2-12 carbon atoms, especially Preferably, it has 2 to 8 carbon atoms, such as propargyl, 3-pentynyl, etc.), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, Phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1 -Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, for example, trimethylsilyl , Triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group Nitro group, alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy A cycloalkyloxy group such as cyclopentyloxy and cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms such as phenoxy and 1-naphthoxy). A heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (Preferably C1-C32, more preferably C1-C18 silyloxy Si group, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetoxy, Pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy, A cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms) , For example, phenoxycarbonyloxy),

  A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group). N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexyl Sulfonyloxy), arylsulfo A ruoxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom). An acyl group having ˜24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms) And, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having 7 to 32 carbon atoms) Preferably charcoal An aryloxycarbonyl group of 7 to 24, for example, phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as carbamoyl, N, N-diethyl Carbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably Is an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. For example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably Is preferably 6 to 32 carbon atoms Is an anilino group having 6 to 24, for example, anilino, N-methylanilino), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 4-pyridylamino) A carbonamide group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably A ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably having 36 or less carbon atoms, more preferably carbon An imide group having a number of 24 or less, for example, N-succinimide group, N-phthalimide group), alcohol Sicarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyl Oxycarbonylamino),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, for example, phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 48 carbon atoms, more Preferably it is a C1-C24 sulfonamide group, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably carbon A sulfamoylamino group having 1 to 48, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably Has 1 to 32 carbon atoms, more preferably 1 to 2 carbon atoms. An azo group, for example, a phenylazo group, a 3-pyrazolylazo group), an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexyl Thio), an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, such as phenylthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a carbon number). 1 to 18 heterocyclic thio groups, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), alkylsulfinyl groups (preferably having 1 to 32 carbon atoms, more preferably having 1 to 32 carbon atoms) 24 alkylsulfinyl groups such as dodecanesulfinyl), arylsulfinyl (Preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably having 1 to 24 carbon atoms) An alkylsulfonyl group, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably having 6 to 48 carbon atoms, More preferably, it is an arylsulfonyl group having 6 to 24 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl group (preferably having 32 or less carbon atoms, more preferably 24 or less carbon atoms). Yl group, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, Phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having a carbon number) 1 to 32, more preferably a phosphinoylamino group having 1 to 24 carbon atoms, such as diethoxyphosphinoylamino, dioctyloxyphosphinoylamino), an alkyloxycarbonyloxy group (preferably having 5 to 30 carbon atoms) And more preferably an alkyloxycarbonyloxy group having 5 to 10 carbon atoms. Etc. The.
These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.
For details, for example, paragraphs 0027 to 0038 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

<<<<< Counter Anion >>>>
When the dye structure is composed of a cation and a counter anion, the counter anion is not particularly limited, but is preferably a non-nucleophilic anion from the viewpoint of heat resistance. As the non-nucleophilic counter anion, known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315 are preferable. Here, the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.
Counter anions include sulfonate anion, carboxylate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborate anion, —CON ⁻ CO—, —CON ^−. At least one selected from SO ₂ −, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ and B ⁻ (CN) ₃ OCH ₃ is preferable. More preferably, it is selected from sulfonate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborate anion, BF ₄ ⁻ , PF ₆ ⁻ , and SbF ₆ ^−. Is at least one kind.
Among these, as the counter anion, a non-nucleophilic anion having a structure represented by the following (AN-1) to (AN-5) is more preferable.

In formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² may be bonded to each other to form a ring.
X ¹ and X ² each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom. 10 to 10 perfluoroalkyl groups, more preferably 1 to 4 carbon perfluoroalkyl groups, and particularly preferably a trifluoromethyl group.

In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
X ³ , X ⁴ and X ⁵ are each independently the same as X ¹ and X ² , and the preferred range is also the same.

In formula (AN-3), X ⁶ represents an alkyl group having 1 to 10 carbon atoms.
X ⁶ is preferably a C 1-10 perfluoroalkyl group, and more preferably a C 1-4 perfluoroalkyl group.

In formula (AN-4), X ⁷ represents an alkylene group having 1 to 10 carbon atoms.
X ⁷ is preferably a C 1-10 perfluoroalkylene group, and more preferably a C 1-4 perfluoroalkylene group.

In formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group.
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently more preferably a halogen atom and / or a phenyl group having an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having a fluorine atom. More preferred are groups.

The non-nucleophilic counter anion also represents —B (CN) _n1 (OR ^a ) _4-n1 (R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents It is preferably an integer of 1 to 4. R ^a as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R ^a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
n1 is preferably 1 to 3, and more preferably 1 or 2.

The non-nucleophilic counter anion is further —PF ₆ R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6). It is preferable that R ^P is preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably an alkyl group having a fluorine atom having 1 to 4 carbon atoms, and further preferably a perfluoroalkyl group having 1 to 3 carbon atoms.
n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.

The mass per molecule of the non-nucleophilic counter anion is preferably from 100 to 1,000, more preferably from 200 to 500.
The dye multimer (A) may contain only one kind of non-nucleophilic counter anion, or may contain two or more kinds.
Specific examples of the non-nucleophilic counter anion are shown below, but the present invention is not limited thereto.

  Specific examples of repeating units having a dye structure that are preferably used in the present invention are shown below. Needless to say, the present invention is not limited to these examples.

<<<<< other repeating unit >>>>
The polymer chain Q may contain other repeating units in addition to the repeating unit having the dye structure described above. Other repeating units may contain a functional group such as a polymerizable group or an acid group. It does not have to contain a functional group. It preferably has at least one selected from repeating units having an acid group and repeating units having a polymerizable group, and more preferably includes a repeating unit having an acid group.

As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), or a methylol group. A group containing an ethylenically unsaturated bond is preferable, and a (meth) acryloyl group is more preferable. The (meth) acryloyl group can be introduced, for example, by reacting glycidyl (meth) acrylate with 3,4-epoxycyclohexylmethyl (meth) acrylate.
When the polymer chain Q includes a repeating unit having a polymerizable group, the ratio of the repeating unit having a polymerizable group is preferably, for example, 5 to 50 mol with respect to 100 mol of all the repeating units of the polymer chain Q, and 10 to 40 Mole is more preferred.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Only one type of acid group may be included, or two or more types of acid groups may be included.
When the polymer chain Q includes a repeating unit having an acid group, the ratio of the repeating unit having an acid group is preferably, for example, 5 to 50 mol, and 10 to 40 mol with respect to 100 mol of all repeating units of the polymer chain Q. More preferred.

Other functional groups include groups consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, development promoting groups such as lactone groups, acid anhydride groups, amide groups and cyano groups, long chain and cyclic alkyl groups, and aralkyls. Groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, maleimide groups, amino group and other affinity control groups, and the like can be introduced as appropriate.
In the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, the number of repeating alkyleneoxy chains is preferably 2 to 10, more preferably 2 to 15 and even more preferably 2 to 10. One alkyleneoxy chain is represented by — (CH ₂ ) _n O—, and n is an integer, but n is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 or 3.

Although the specific example of another repeating unit is shown, this invention is not limited to this.

<<< Polymer chain containing no dye structure >>>
The dye multimer (A) may have a polymer chain that does not contain a dye structure.
Examples of the polymer chain not including the dye structure include a polymer chain composed of the repeating units described in the other repeating units of the polymer chain Q described above.

<< Various Properties of Dye Multimer (A) >>
The weight average molecular weight of the dye multimer (A) is preferably 1000 to 100,000. For example, the lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more. The upper limit is more preferably 50000 or less, still more preferably 20000 or less, and even more preferably 15000 or less. If the weight average molecular weight is in the above range, the color transfer is better. Furthermore, the developability is improved and the generation of development residues can be further reduced.

  The acid value of the dye multimer (A) is preferably 10 mgKOH / g or more. The lower limit is more preferably 15 mgKOH / g or more, and still more preferably 20 mgKOH / g or more. The upper limit is more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less. If the acid value is 10 mgKOH / g or more, the developability is improved and the generation of development residues can be further reduced.

The specific absorbance of the dye multimer (A) is measured, for example, by using a solvent having sufficient solubility in the dye multimer (A) so that the maximum absorbance at 400 nm to 800 nm is 1.0. And adjusting the concentration of the solution containing the dye multimer (A) and measuring the absorbance of this solution at 25 ° C. using a cell having an optical path length of 1 cm. As the solvent for measuring the specific absorbance, a solvent having sufficient solubility for the dye multimer (A) can be appropriately used. Preferred solvents include tetrahydrofuran, methanol, isopropyl alcohol, dimethyl sulfoxide, acetonitrile, ethyl acetate, hexane, toluene, water, concentrated sulfuric acid, methanesulfonic acid and the like. Tetrahydrofuran is used when tetrahydrofuran has sufficient solubility.
The specific absorbance represented by the following formula (Aλ) at the maximum absorption wavelength at 400 nm to 800 nm is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and particularly preferably 30 or more. If the specific absorbance is 5 or more, it can be suitably used as a colorant.
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml.

The dye multimer (A) is preferably a dye. The dye refers to a pigment having substantial solubility in water or an organic solvent, and is particularly preferably an organic solvent-soluble dye that is soluble in the following organic solvents.
Examples of the organic solvent include esters (eg, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate). , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (for example, toluene, xylene, etc.) and the like. It is preferable to dissolve 1 to 50% by mass with respect to the solvent, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. By being in this range, when the colored composition of the present invention is applied to the production of a color filter or the like, the coated surface shape is suitable, and the concentration reduction due to elution after application of other colors can be further reduced.

  In the colored composition of the present invention, the dye multimer (A) may be used alone or in combination of two or more.

The content of the dye multimer (A) in the colored composition of the present invention is set in consideration of the content ratio with other dyes (preferably pigments) described later.
The mass ratio of the dye multimer to the pigment (dye multimer (A) / pigment) is preferably 0.1 to 5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.
The content of the dye multimer (A) in the colored composition of the present invention is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and more preferably 10 to 25% by mass with respect to the total solid content of the colored composition. Is particularly preferred.

<< Synthesis Method of Dye Multimer (A) >>
The method for producing the dye multimer represented by the general formula (1) is not particularly limited, but a polyfunctional thiol compound having 3 to 10 thiol groups in one molecule, a dye structure and a radical polymerizable group It can manufacture by the method of radical-polymerizing the compound which has. Hereinafter, a compound having a dye structure and a radical polymerizable group is also referred to as a “radical polymerizable dye compound”.
In the radical polymerizable dye compound, examples of the dye structure include those described above. In the radical polymerizable dye compound, examples of the radical polymerizable group include groups containing an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
More specifically, a method of radical polymerization of the compound represented by the general formula (3) and a radical polymerizable dye compound is preferable.
P ⁰ − (SH) _n (3)
In general formula (3), P ⁰ represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.

In the general formula (3), P ⁰ is 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And groups consisting of 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
The n-valent linking group represented by P ⁰ is 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And groups consisting of 0 to 10 sulfur atoms are preferred. More preferably, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 atoms. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.
The n-valent linking group represented by P ⁰ is preferably a linking group derived from a polyhydric alcohol.
The compound represented by the general formula (3) is preferably a compound represented by the general formula (4).
A ^0- (B ⁰ -C ⁰ -SH) _n (4)
In general formula (4), A ⁰ represents an n-valent linking group,
B ⁰ represents a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—,
R represents a hydrogen atom, an alkyl group or an aryl group,
C ⁰ represents a single bond or a divalent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.
A ⁰ , B ⁰ and C ⁰ in the general formula (4) are respectively synonymous with the ranges described for A ¹ , B ¹ and C ¹ in the general formula (2), and preferred embodiments are also the same.
Specific examples of the compound represented by the general formula (3) include the following compounds.

  Among these, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, particularly preferred compounds are (SH-1) to (SH-8), (SH-16) to (SH-). 20) and (SH-22) to (SH-32) are preferable.

  The radical polymerization of the polyfunctional thiol compound and the radical polymerizable dye compound is performed by, for example, dissolving the polyfunctional thiol compound and the radical polymerizable dye compound in an appropriate solvent, adding a radical generator to the solution, It can carry out using the method (thiol-ene reaction method) of adding at about 50 to 100 degreeC.

Examples of suitable solvents used in the thiol-ene reaction method can be arbitrarily selected depending on the solubility of the polyfunctional thiol compound and the radical polymerizable dye compound.
For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  In addition, as radical generators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate Azo compounds such as benzoyl peroxide, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

<< polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by a radical, an acid, or heat can be used. For example, a compound having a group having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group and the like can be mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. In the present invention, the polymerizable compound is preferably a 3-6 functional (meth) acrylate compound.
The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer (ie, a dimer, a trimer and an oligomer), or a mixture thereof and a multimer thereof.

Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

  The polymerizable compound is also preferably a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. As examples thereof, for example, compounds described in paragraph 0227 of JP2013-29760A and paragraph numbers 0254 to 0257 of JP2008-292970A can be referred to, and the contents thereof are incorporated in the present specification.

  The polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, SR454, SR499 commercially available from Sartomer) preferable. These oligomer types can also be used. Preferred embodiments of the polymerizable compound are shown below.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. An ester having a group is more preferable, and particularly preferable is an ester in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

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

As the polymerizable compound, a compound having a structure derived from a cyclic ester (for example, caprolactone, valerolactone and the like, and caprolactone is particularly preferable) is also a preferable embodiment.
The compound having a structure derived from caprolactone is not particularly limited as long as it has a structure derived from caprolactone in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone-modified polyhydride obtained by esterifying polyhydric alcohols such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Mention may be made of functional (meth) acrylates. Among these, a compound having a structure derived from caprolactone represented by the following general formula (Z-1) is preferable.

  In general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In 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 bond.

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

The polymerizable compound having a structure derived from caprolactone is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1, the number of groups represented by formula (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, represented by formula (Z-2) Number of groups = 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, R ¹ is all hydrogen atoms And the like, and DPCA-120 (a compound in which m = 2, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).

  As the polymerizable compound, a compound represented by the following general formula (Z-4) or (Z-5) can also be used.

In general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O). -, Y represents each independently an integer of 0 to 10, and X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. . However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (Z-5), the total of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. . However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total 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.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen A form in which the end on the atom side is bonded to X is preferred.

  The compound represented by general formula (Z-4) or general formula (Z-5) may be used individually by 1 type, and may be used together 2 or more types. In particular, in the general formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

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

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), among which exemplary compounds (a) and ( b), (e) and (f) are preferred.

  As a commercial item of the polymerizable compound represented by the general formula (Z-4) or the general formula (Z-5), for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Japan Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

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

In the present invention, a compound having an epoxy group preferably has a structure in which two benzene rings are connected by a hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.
Moreover, it is preferable that the epoxy group is connected via a connecting group. As the linking group, an alkylene group, an arylene group, -O-, -NR '-(R' is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. And a group containing at least one selected from a structure represented by —SO ₂ —, —CO—, —O— and —S—.

  The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably from 100 to 400 g / eq, and from 100 to 300 g. More preferably, it is / eq. The said effect is acquired by making the upper limit of the epoxy equivalent of the compound which has an epoxy group into 500 g / eq or less. Moreover, it is preferable from practical stability that the lower limit of the epoxy equivalent of the compound which has an epoxy group shall be 100 g / eq or more.

  The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). 200-100000 are preferable and, as for the weight average molecular weight of the compound which has an epoxy group, 500-50000 are more preferable.

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

In General Formula (2a), R ^{1 to} R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
For details of R ^{1 to} R ^{19 in} the general formula (2a), paragraph number 0036 of JP2013-011869A can be referred to, and the contents thereof are included in the present specification.
In particular, R ^{1 to} R ¹⁹ are preferably each independently a hydrogen atom, a methyl group, an ethyl group, or a methoxy group. More preferably, at least one selected from R ¹³ , R ¹⁸ and R ¹⁹ is a methyl group. More preferably, R ¹³ , R ¹⁸ and R ¹⁹ are methyl groups, and R ^{1 to} R ¹² and R ^{14 to} R ¹⁷ are hydrogen atoms.
The compound represented by the general formula (2a) can be synthesized in consideration of paragraph number 0036 of JP2013-011869A. Examples of commercially available products include VG-3101L manufactured by Printec Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd.

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

In the formula (EP1), R ^{EP1 to} R ^EP3 each represents a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R ^EP1 and R ^EP2 and R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure.
^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 to R ^EP3 combines with Q ^EP may form a ring structure.
n ^EP represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. However, n ^EP is 2 when Q ^EP is a single bond.
The details of R ^{EP1 to} R ^EP3 and Q ^EP can be referred to the description of paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein.

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

As the compound having an epoxy group, an oligomer or polymer having an epoxy group in the side chain can also be preferably used. Examples of such compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic epoxy resins.
These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.
As a commercial product, for example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku) As a phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 The above-mentioned cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690. EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and aliphatic epoxy resins include ADEKA RESIN EP-4080S, E -4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
Also, JER1031S (manufactured by Mitsubishi Chemical Corporation), JER1032H60 (manufactured by Mitsubishi Chemical Corporation), EPICLON HP-4700 (manufactured by DIC Corporation), EPICLON N-695 (manufactured by DIC Corporation), EPICLON840 ( DIC Corporation), EPICLON N660 (DIC Corporation), EPICLON HP7200 (DIC Corporation), and the like can also be preferably used.

In the present invention, examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. And urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Thus, a colored composition having an extremely excellent photosensitive speed can be obtained.
In the present invention, a compound having an oxetane group can also be used as the polymerizable compound. Examples of the compound having an oxetane group include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein. As specific examples, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  In the colored composition of the present invention, the content of the polymerizable compound is preferably 0.1 to 30% by mass with respect to the total solid content of the colored composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 20% by mass or less, and further preferably 15% by mass or less. One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<< Polyfunctional thiol compound >>
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. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
General formula (T1)

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

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

  When the coloring composition of this invention contains a polyfunctional thiol, 0.3-8.9 mass% is preferable with respect to the total solid of a coloring composition, and 0.8-6 More preferably, 4% by mass. Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.

<< Other dyes >>
The coloring composition of the present invention may contain a dye other than the above-described dye multimer (A) (hereinafter also referred to as other dye). As the other coloring matter, either a pigment or a dye can be preferably used, and a pigment is more preferred because of its high resistance to heat and light.
The content of other pigments is preferably 95% by mass or more, more preferably 97% by mass or more, and still more preferably 99% by mass or more with respect to the total amount of other pigments. . According to this aspect, it is easy to obtain an effect of increasing resistance to heat and light.
As the pigment, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferred.

<<< Dye >>>
There is no restriction | limiting in particular as dye, The well-known dye currently used for the color filter can be used. For example, JP-A 64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Toho 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No., U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. The chemical structure includes pyrazole azo, pyromethene, anilinoazo, triarylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc. Dyes can be used.

<<< Pigment >>>>
Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like, or carbon black (CI Pigment Black 7). Specific examples of the metal compound include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal composite oxides.

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,167,171,175,176,177,179,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1; and the like.

The organic pigments can be used alone or in various combinations in order to adjust the spectrum and increase the color purity. Specific examples of preferred combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them and a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment And the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50, and more preferably in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the desired spectrum.
As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, and more preferably 100: 30 to 100: 120.
As the blue pigment, a phthalocyanine pigment alone or a mixture of this with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100.
As the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture of two or more of these is used, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

When used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast. Moreover, it is preferable that it is 5 nm or more from a viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle size of the pigment can be measured by a known method such as an electron microscope.
Among these, the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments. In particular, C.I. I. Pigment red 177 (anthraquinone pigment), C.I. I. Pigment red 254 (diketopyrrolopyrrole pigment), C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment Blue 15: 6 (phthalocyanine pigment), C.I. I. Pigment yellow 138 (quinophthalone pigment), C.I. I. Pigment yellow 139,185 (isoindoline pigment), C.I. I. Pigment yellow 150 (azomethine pigment), C.I. I. Pigment violet 23 (dioxazine pigment) is particularly preferred.

When the coloring composition of the present invention contains other pigments, the content of the other pigments is preferably 10 to 70% by mass, and more preferably 25 to 65% by mass with respect to the total solid content of the coloring composition. 35-55 mass% is still more preferable.
The coloring composition of the present invention may contain only one type of other pigment or two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Resin >>
The colored composition of the present invention preferably contains a resin. Examples of the resin include a resin (dispersion resin) for dispersing a pigment, an alkali-soluble resin, and the like.

<<< Dispersed resin >>>
Examples of the dispersion resin include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene. Examples thereof include polymer dispersants such as sulfonic acid formalin condensate.
From the structure, the polymer dispersant further comprises a linear polymer, a terminal-modified polymer having an anchor site to the pigment surface, a graft polymer having an anchor site to the pigment surface, and an anchor site to the pigment surface. It can be classified into a block type polymer having.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include, for example, polymers having a phosphate group at the terminal described in JP-A-3-112992 and JP-T-2003-533455, and JP-A-2002. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include polyester resins. Specifically, reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like, A reaction product of polyallylamine and polyester described in JP-A-169821 and the like, a copolymer of a macromonomer described in JP-A-10-339949 and JP-A-2004-37986, and a nitrogen atom monomer, JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like, graft-type polymers having a partial skeleton or a heterocyclic ring of organic dyes, JP-A-2010-106268, etc. And a copolymer of the described macromonomer and acid group-containing monomer. In particular, the amphoteric resin having a basic group and an acid group described in JP-A-2009-203462 has the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion. Particularly preferable from the viewpoint.

  As the macromonomer used when the graft polymer is produced by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 manufactured by Toa Gosei Co., Ltd. (polymethacrylic group whose terminal group is a methacryloyl group). Acid methyl), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polyester whose terminal group is a methacryloyl group) Butyl acrylate), Placel FM5 manufactured by Daicel Chemical Industries, Ltd. (2-hydroxyethyl methacrylate, ε-caprolactone 5-molar equivalent addition product), FA10L (2-hydroxyethyl acrylate, ε-caprolactone 10 molar equivalent addition product) ) And polyesters described in JP-A-2-272009 Macromonomer etc. are mentioned. Among these, a polyester-based macromonomer that is particularly excellent in flexibility and solvent affinity is preferable from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion. A polyester macromonomer represented by the polyester macromonomer described in Kaihei 2-272009 is particularly preferable.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The resin is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, and 107 (carboxylic acid ester). ), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (non-high molecular weight) Saturated polycarboxylic acid) "," EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (manufactured by EFKA) High molecular weight polycarboxylate), 6220 (fatty acid polyester) Tel), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer), Polyflow No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703, manufactured by Enomoto Kasei Co., Ltd. −50, DA-705, DA-725 ”,“ Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”manufactured by Kao Corporation,“ Homogenol L-18 (polymeric polycarboxylic acid), Emulgen 920, 93 , 935, 985 (polyoxyethylene nonylphenyl ether), acetamine 86 (stearylamine acetate), “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), manufactured by Nippon Lubrizol Co., Ltd.” 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate) ”manufactured by Nikko Chemical Co., MYS- “IEX (polyoxyethylene monostearate)”, “Hinoact T-8000E etc.” manufactured by Kawaken Fine Chemical Co., Ltd., “organosiloxane polymer KP341” manufactured by Shin-Etsu Chemical Co., Ltd., “W001” manufactured by Yusho Co., Ltd. : Cationic surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan Nonionic surfactants such as fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 100” manufactured by Morishita Sangyo Co., Ltd. Polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disp Aid 15 manufactured by San Nopco Co., Ltd. Polymer dispersants such as “SEAIDE 9100”, manufactured by ADEKA Corporation “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 "," Ionet (trade name) S-20 "manufactured by Sanyo Chemical Co., Ltd., and the like.

Resin may be used independently and may be used in combination of 2 or more type. The resin is described later together with a terminal-modified polymer having an anchor site to the pigment surface, a graft polymer having an anchor site to the pigment surface, and a block polymer having an anchor site to the pigment surface. An alkali-soluble resin may be used in combination.
Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples include acidic cellulose derivatives having a resin, and resins having a hydroxyl group modified with an acid anhydride. Particularly preferred is a (meth) acrylic acid copolymer. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.

  In the coloring composition, when the dispersion resin is contained, the content of the dispersion resin is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. For example, the lower limit is more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more. For example, the upper limit is more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less.

<<< Alkali-soluble resin >>>
The coloring composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation are improved. In addition, alkali-soluble resin can also be used as a dispersion resin mentioned above.
The molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000.
The alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.

The alkali-soluble resin will be described.
The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the alkali-soluble resin, a polymer having a carboxylic acid in the 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, and a partial esterification are used. Examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing a polymerizable group in a side chain is useful.
The alkali-soluble resin containing a polymerizable group is prepared by reacting an isocyanate group and a hydroxyl group in advance, leaving one unreacted isocyanate group and containing a polymerizable group such as a (meth) acryloyl group, and a carboxyl group. Urethane-modified alkali-soluble resin obtained by reacting with an acrylic resin containing; an alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond in the molecule; acid Pendant-type epoxy acrylate resin; alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a dibasic acid anhydride having a polymerizable double bond; an acrylic resin containing a hydroxyl group, an isocyanate and a polymerizable group An alkali-soluble resin obtained by reacting a compound; Basic treatment of a resin having in the side chain an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2002-229207 and JP-A-2003-335814 An alkali-soluble resin obtained by the following:
Examples of the alkali-soluble resin containing a polymerizable group include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, KS resist). 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure-RD-F8 (Nippon Catalyst) Etc.).

  Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 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 A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

  The alkali-soluble resin is a monomer containing a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer (a) obtained by polymerizing the components.

In 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.
General formula (ED2)

In 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), the description of JP 2010-168539 A can be referred to.

In the general formula (ED), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, but for example, methyl, ethyl, n Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl , Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoe Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butylsilane) Rohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, 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-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

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

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 that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the formula (X), the number of carbon atoms of the alkylene group R ₂ is preferably 2-3. Moreover, although the carbon number of the alkyl group of R < ₃ > is 1-20, Preferably it is 1-10, and the alkyl group of R < ₃ > may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

Regarding the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. It is incorporated herein.
Furthermore, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, No. 024934, paragraph numbers 0132 to 0143 described in paragraphs 0132 to 0143 and the binder resins used in the examples, JP 2011-242752A paragraphs 0092 to 0098 and the binder resins used in the examples, Paragraph No. of Kokai 2012-032770 It is also possible to use a binder resin according to 030-0072. These contents are incorporated herein.

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

  When the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, based on the total solid content of the coloring composition. 10 mass% is still more preferable. The coloring composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Pigment derivative >>
The coloring composition of the present invention can contain a pigment derivative.
The pigment derivative is a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a phthalimidomethyl group, or the like. The pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.
Examples of the pigment for constituting the pigment derivative include pyrrolopyrrole pigment, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, Indolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments and the like can be mentioned.
As an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
1-50 mass% is preferable with respect to the total mass of a pigment, and, as for content of a pigment derivative, 3-30 mass% is more preferable. The pigment derivative may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< photopolymerization initiator >>
The colored composition of the present invention may further contain a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

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

  From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Particularly preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

In particular, when the colored composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, stepper exposure is used for curing exposure. This exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of the photopolymerization initiator low. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferable examples of the photopolymerization initiator include oxime compounds.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane 2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660, J. MoI. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In 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 General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic 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. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In general formula (OX-1), as a bivalent organic group represented by A, a C1-C12 alkylene group, a cycloalkylene group, and an alkynylene group are preferable. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

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

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. For example, in a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent is used and the concentration is 0.01 g / L. It is preferable to measure.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

When the coloring composition of this invention contains a photoinitiator, 0.1-50 mass% is preferable with respect to the total solid of a coloring composition, More preferably, it is 0.5. It is -30 mass%, More preferably, it is 1-20 mass%. Within this range, better sensitivity and pattern formability can be obtained.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< other ingredients >>
In addition to the above-mentioned components, the coloring composition of the present invention is a range that does not impair the effects of the present invention. And other components may be included.

<<< Organic solvent >>>
The coloring composition of the present invention may contain a solvent.
The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but the solubility, coating property, and safety of the dye multimer (A), the polymerizable compound, etc. are improved. It is preferable to select in consideration.

As a solvent,
Esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate ( Examples: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (eg Methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), 2- Oxypropio Acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid) Propyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methylpropionate) Acid methyl, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.
As ketones, for example, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, and the like,
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these solvents from the viewpoints of solubility of the dye multimer (A), the polymerizable compound, and the like, and improvement of the coating surface condition. For example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl carbitol acetate A mixed solution composed of two or more selected from butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.

The content of the solvent is preferably such that the total solid concentration of the colored composition is 5 to 80% by mass from the viewpoint of applicability. For example, the lower limit is more preferably 5% by mass or more, and still more preferably 10% by mass or more. For example, the upper limit is more preferably 60% by mass or less, and still more preferably 50% by mass or less.
The colored composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< crosslinking agent >>>
The coloring composition of the present invention may contain a crosslinking agent. By containing a crosslinking agent, the hardness of the cured film obtained can be further increased.
The crosslinking agent is not particularly limited as long as it can cure the film by a crosslinking reaction. For example, (a) an epoxy resin, (b) a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, c) A phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, reference can be made to the descriptions in paragraphs 0134 to 0147 of JP-A No. 2004-295116, the contents of which are incorporated herein.
When the coloring composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass, and 3 to 20% by mass with respect to the total solid content of the coloring composition. % Is more preferable.
The coloring composition of the present invention may contain only one type of crosslinking agent or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< Polymerization inhibitor >>>
In the colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned.
When the coloring composition of this invention contains a polymerization inhibitor, about 0.01-5 mass% is preferable with respect to the mass of a coloring composition.
The coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< surfactant >>>
Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

  For example, by containing a fluorinated surfactant, the liquid properties (particularly fluidity) when prepared as a coating solution are further improved. That is, in the case of forming a film using a coloring composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, The coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Rusupasu 20000 (Lubrizol Japan Co., 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.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

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

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

When the coloring composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.001%, based on the total mass of the coloring composition. 005 to 1.0% by mass.
The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<<< Organic carboxylic acid, organic carboxylic acid anhydride >>>
The coloring composition of the present invention may contain an organic carboxylic acid and / or an organic carboxylic acid anhydride. The molecular weight of the organic carboxylic acid or organic carboxylic acid anhydride is preferably 1000 or less. As specific examples of the organic carboxylic acid and the organic carboxylic acid anhydride, for example, paragraphs 0338 to 0340 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
When the coloring composition of the present invention contains an organic carboxylic acid and / or an organic carboxylic acid anhydride, the content of the organic carboxylic acid and / or the organic carboxylic acid anhydride is based on the total solid content of the coloring composition. 0.01-10 mass% is preferable, 0.03-5 mass% is more preferable, 0.05-3 mass% is still more preferable.
The colored composition of the present invention may contain only one type of organic carboxylic acid and / or organic carboxylic acid anhydride, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Various additives, for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended with the colored composition of the present invention as necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116, the contents of which are incorporated herein.
The coloring composition of the present invention can contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the publication.

<Method for preparing colored composition>
The coloring composition of the present invention is prepared by mixing the aforementioned components.
In preparing the colored composition, the components constituting the colored composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth coloring composition in a post process.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

  The colored composition of the present invention can be suitably used for forming a colored layer of a color filter because it can form a cured film having good light resistance, color transfer and flatness. Further, the colored composition of the present invention is a colored pattern such as a color filter used in a solid-state imaging device such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), or an image display device such as a liquid crystal display device. It can be suitably used for forming. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. Especially, it can use suitably for manufacture of the color filter for solid-state image sensors, such as CCD and CMOS.

<Color filter, pattern formation method, color filter manufacturing method>
Next, the color filter, pattern forming method and color filter of the present invention will be described in detail through the manufacturing method. A method for producing a color filter using the pattern forming method of the present invention will also be described.

The color filter of the present invention is obtained by using the colored composition of the present invention.
In the pattern forming method of the present invention, the colored composition of the present invention is applied onto a support to form a colored composition layer, and unnecessary portions are removed to form a colored pattern.
The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern of a color filter.
In the pattern forming method of the present invention, pattern formation may be performed by a so-called photolithography method, or pattern formation may be performed by a dry etching method.
That is, the first aspect of the method for producing a color filter of the present invention includes a step of applying the colored composition of the present invention on a support to form a colored composition layer, and exposing the colored composition layer in a pattern. And a step of developing and removing the unexposed portion to form a colored pattern. As needed, you may provide the process (prebaking process) of baking a coloring composition layer, and the process (post-baking process) of baking the developed coloring pattern.
The second aspect of the method for producing a color filter of the present invention includes a step of applying the colored composition of the present invention on a support to form a colored composition layer and curing to form a colored layer; A step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and forming a colored pattern by dry etching the colored layer using the resist pattern as an etching mask Including the step of.
The color filter of the present invention can be suitably obtained by the above production method. These details are described below.

<< Step of Forming Colored Composition Layer >>
In the step of forming the colored composition layer, the colored composition layer is formed on the support by applying the colored composition of the present invention.

As the support, for example, a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
The colored pattern in the present invention may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface).
If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a method for applying the colored composition of the present invention on the support, various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be used.

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

<< When pattern is formed by photolithography (first aspect) >>
<<< Exposure process >>>
Next, the colored composition layer formed on the support is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the colored composition layer formed on the support using a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 30~1500mJ / cm ^2, more preferably 50~1000mJ / cm ^2, and most preferably 80~500mJ / cm ^2.

  The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and further preferably 0.2 to 0.8 μm. By setting the film thickness to 1.0 μm or less, high resolution and high adhesion can be easily obtained.

<<< Pattern formation process >>>
Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming step). The development removal of the unexposed portion can be performed using a developer. Thereby, the coloring composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. , Organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

It is preferable to perform heat treatment (post-bake) after development and drying. If a multicolor coloring pattern is formed, a cured film can be produced by sequentially repeating the process for each color. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for complete curing, and the heating temperature is preferably, for example, 100 to 240 ° C, more preferably 200 to 240 ° C.
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 dryer) or a high-frequency heater so that the film after development is in the above condition. it can.

<< When pattern is formed by dry etching method (second embodiment) >>
The pattern formation by the dry etching method is performed by curing the colored composition layer formed on the support to form a colored layer, and then using the patterned photoresist layer as a mask to etch the obtained colored layer. Can be used.
Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming the photoresist layer, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable.

As the photoresist layer, for example, a positive radiation sensitive composition sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), excimer lasers, deep ultraviolet rays, electron beams, ion beams and X rays. Is preferably used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is more preferable.
Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to produce a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolving power, it is used for manufacturing integrated circuits such as IC (integrated circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. As a commercial item, "FHi622BC" (made by FUJIFILM Electronics Materials) etc. are mentioned, for example.

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and further preferably 0.3 to 2 μm. In addition, the application method of a positive type radiation sensitive composition can be suitably performed using the application method in the above-mentioned colored layer.

  Next, by exposing and developing the photoresist layer, a resist pattern (patterned photoresist layer) provided with a group of resist through holes is formed. The formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the colored layer.

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

  Any developer can be used as long as it does not affect the colored layer and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, a combination of various solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, and 1,8-diazabicyclo [5,4,0] -7-undecene. When an alkaline aqueous solution is used, a washing treatment with water is generally performed after development.

  Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that the through hole group is formed in the colored layer. Thereby, a colored pattern is formed. The through-hole group is preferably provided in a checkered pattern, for example, in the colored layer. Therefore, the first colored pattern in which the through hole group is provided in the colored layer has a plurality of square-shaped first colored pixels in a checkered pattern.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first-stage etching is performed according to the etching time calculated in (2) above.
(4) The second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.

The mixed gas used in the first stage etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed. Further, in the second stage etching process and the over etching process, after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

  It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.

  Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

  Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.

  Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

  Examples of the process of removing the resist pattern using the cleaning water include a process of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.

  The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

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

  The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably contains at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

  When removing with a stripping solution, it is sufficient that the resist pattern formed on the colored pattern has been removed, and even when the deposit is an etching product on the side wall of the colored pattern, the deposit is completely removed. It may not be removed. A deposit means an etching product deposited and deposited on the side wall of a colored layer.

  As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

  The manufacturing method of the color filter of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as a process other than the above as needed. For example, after performing the coloring composition layer forming step, the exposure step, and the pattern forming step described above, a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary.

In addition, the solvent for the colored composition of the present invention is used to efficiently clean the nozzles and pipes of the discharge unit of the coating apparatus, and the contamination of the colored composition and the pigment due to adhesion, settling, and drying in the coating machine. Is preferably used as the cleaning liquid. JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can be suitably used.
Of the above, 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 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and 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. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid to contaminants, the above-described surfactant relating to the colored composition of the present invention may be added to the cleaning liquid.

Since the color filter of the present invention uses the colored composition of the present invention, the color filter is excellent in light resistance, color transfer and flatness.
The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

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

On the support, there are a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon, etc., and the photodiode is placed on the transfer electrode. A light-shielding film made of tungsten or the like that is open only in the light-receiving part, and a device protective 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 part. Further, the color filter for a solid-state image sensor according to the present invention is provided.
Further, a configuration having a light collecting means (for example, a micro lens, etc., the same applies hereinafter) on the device protection layer and under the color filter (on the side close to the support), a structure having the light collecting means on the color filter, etc. It may be.

<Image display device>
The color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device. It is particularly suitable for liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. 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, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

In addition to the color filter of the present invention, the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Have been described.

  When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue light emitting diode (LED) light sources By using a backlight, a liquid crystal display device having high luminance and high color purity and excellent color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Unless otherwise specified, “%” and “parts” are based on mass.

<Synthesis of Xanthene Compound (A-xt-1)>

<< Synthesis of Intermediate 1 >>
31 parts of 3,6-dichlorosulfofluorane (DCSF) (manufactured by Chugai Kasei), 67 parts of 2,6-diisopropylaniline, 17 parts of zinc chloride and 120 parts of sulfolane were placed in a flask and stirred at an external temperature of 200 ° C. for 8 hours. . Thereafter, the mixture was allowed to cool to room temperature, the reaction solution was added dropwise to 600 parts of 2N aqueous hydrochloric acid, and the precipitated crystals were filtered off. The crystals were dispersed and washed with 600 parts of acetonitrile at 40 degrees, filtered, and air-dried for 10 hours to obtain 42.5 parts of intermediate 1 (yield: 82%).
<< Synthesis of Intermediate 2 >>
11 parts of Intermediate 1 and 50 parts of phosphorus oxychloride were placed in a flask and stirred at 60 ° C. for 4 hours. The mixture was allowed to cool to room temperature, and the reaction solution was added dropwise to 150 parts of ice water and stirred for 30 minutes. The obtained crystals were filtered off and washed with 20 parts of water. Thereafter, the obtained crystals were dissolved in 150 parts of chloroform and filtered through Celite. The filtrate was separated and washed with 100 parts of 5% saline and 100 parts of 15% saline. The filtrate was dried over sodium sulfate and concentrated under reduced pressure to obtain 12.1 parts of intermediate 2 (yield: 91%).
<< Synthesis of Intermediate 3 >>
15 parts of pentafluorobenzenesulfonyl chloride and 300 parts of tetrahydrofuran (THF) were placed in a flask, and the internal temperature was cooled to -10 ° C. Thereto, 6.8 parts of 28% aqueous ammonia was added dropwise so that the reaction solution maintained at 0 ° C. or lower. After dropping, the reaction solution was filtered after stirring at 0 ° C. for 1 hour. The obtained filtrate was concentrated under reduced pressure to remove THF, and then 100 parts of water was added and stirred. The obtained solid was filtered, washed with water, and then blown and dried for 10 hours to obtain 11.7 parts of intermediate 3 (yield: 84%).
<< Synthesis of Intermediate 4 >>
15 parts of Intermediate 3, 4.9 parts of 2-mercaptoethanol, and 100 parts of methanol were added to the flask and stirred at room temperature. Thereto, 6.5 parts of triethylamine was added dropwise so that the temperature of the reaction solution did not exceed 30 ° C. After stirring this reaction liquid at room temperature for 1 hour and concentrating under reduced pressure, 90 parts of ethyl acetate, 80 parts of saturated salt solution, and 10 parts of saturated sodium hydrogen carbonate solution were added thereto, and liquid separation operation was performed. After extracting the aqueous layer with 90 parts of ethyl acetate, magnesium sulfate was added to the obtained organic layer. After filtration, the filtrate was concentrated under reduced pressure and blown and dried for 10 hours to obtain 17 parts (yield: 92%) of Intermediate 4.
<< Synthesis of Intermediate 5 >>
49 parts of Intermediate 4, 25 parts of 2-isocyanatoethyl acrylate (AOI, Showa Denko), 0.2 part of dibutylhydroxytoluene (BHT), 95 parts of dimethylacetamide, Neostan U-600 (manufactured by Nitto Kasei) 1 part was added and it stirred at 85 degreeC for 1 hour. Subsequently, 500 parts of ethyl acetate and 500 parts of saturated saline were added thereto to carry out a liquid separation operation. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure. The obtained solid was suspended and washed with 170 parts of chloroform, filtered, and blown and dried to obtain 60 parts of intermediate 5 (yield: 84%).
<< Synthesis of Xanthene Compound (A-xt-1) >>
5 parts of Intermediate 5, 50 parts of methylene chloride and 3.4 parts of triethylamine were added to the flask and stirred at room temperature. Thereto was added 10.8 parts of Intermediate 2 and stirred at room temperature for 2 hours. After completion of the reaction, 200 parts of chloroform, 500 parts of pure water and 200 parts of saturated saline were added to carry out a liquid separation operation. Sodium sulfate was added to the obtained organic layer and dehydrated, followed by filtration, and the filtrate was concentrated under reduced pressure. The obtained solid was dissolved in chloroform, and purified by column chromatography using a chloroform / ethyl acetate solvent to obtain 12.5 parts (yield: 86%) of A-xt-1.

<Xanthene compounds (A-xt-2), (A-xt-4), (A-xt-6), (A-xt-7), (A-xt-9), (A-xt-12) Synthesis Example of (A-xt-15)>
Xanthene compounds (A-xt-2), (A-xt-4), (A-xt-6), (A-xt-7), (A-xt-9), (A-xt-12), (A-xt-15) was synthesized following the xanthene compound (A-xt-1).

<Synthesis of Dye Multimer Represented by General Formula (1)>
[Synthesis of Dye Multimer S-1]

1.0 part of polyfunctional thiol (compound having the above structure (SH-1), SC Organic Chemical Industry Co., Ltd.), 13.7 parts of xanthene compound (A-xt-1), methacrylic acid (MAA) 2. A mixed solution of 1 part and 9.0 parts of cyclohexanone was heated to 80 ° C. under a nitrogen stream. To this, 0.254 part of 2,2′-azobis (isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemical Industries, Ltd.] was added, followed by heating and stirring at 80 ° C. for 2 hours. Further, 0.254 part of V-601 was added, and the mixture was stirred with heating at 80 ° C. for 2 hours, and further stirred with heating at 90 ° C. for 2 hours. After cooling to room temperature, 30.7 parts of cyclohexanone, 0.32 part of tetrabutylammonium bromide (TBAB), and 1.8 parts of glycidyl methacrylate (GMA) were added, and the mixture was heated and stirred at 80 ° C. for 18 hours. After cooling to room temperature, the reaction solution was dropped into a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and reprecipitated to obtain Dye Multimer S-1.
The weight average molecular weight (polystyrene equivalent value) of the dye multimer S-1 was 14500, and the acid value was 40 mgKOH / g by titration with a 0.1N sodium hydroxide aqueous solution.
The number of repeating units having a dye structure of the polymer chain Q in NMR (nuclear magnetic resonance) measurement was calculated to be an average of 4.5. In addition, a solution containing 0.01 mg / ml of the dye multimer S-1 was prepared by dissolving in tetrahydrofuran (THF) (concentration adjusted so that the maximum absorbance was 1.0). When the absorbance was measured using a cell having an optical path length of 1 cm, the maximum absorption wavelength (λmax) was 535 nm, and the specific absorbance at the maximum absorption wavelength (λmax) was 44.

[Synthesis of Dye Multimer S-2 to 52]
According to the synthesis method of the dye multimer S-1, except that the polyfunctional thiol, the kind and amount of various monomers, the amount of V-601, the amount of GMA, and the amount of TBAB were changed to the following table, the dye multimer S-1 -2 to S-52 were obtained.

<Measurement of specific absorbance>
Each dye multimer is dissolved in tetrahydrofuran (THF) to adjust the concentration so that the maximum absorbance at a wavelength of 400 nm to 800 nm is 1.0. , Based on the following formula (Aλ).
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml.

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

Comparative dyes (S′-1), (S′-2), (S′-3): the following structures

(Synthesis of Comparative Dye (S′-3))

A triarylmethane compound (A-tp-101) was synthesized according to the method described in JP-A No. 2000-162429.
A triarylmethane compound (A-tp-101) (15 g), hydroxyethyl methacrylate (10 g), methacrylic acid (5.5 g), and azobisisobutyronitrile (5 g) were added to N-ethylpyrrolidone (70 g). In addition, the mixture was stirred and dissolved at room temperature for 30 minutes (polymerization solution for dropping).
Separately, a triarylmethane compound (A-tp-101) (15 g), hydroxyethyl methacrylate (10 g), and methacrylic acid (5.5 g) were placed in a container and dissolved, and stirred at 80 ° C. The polymer solution for dripping prepared there was dripped over 3 hours, and after stirring for 1 hour, azoisobutyronitrile (2.5g) was added, and it was made to react for 2 hours, and was stopped. After cooling to room temperature, the solvent was distilled off to obtain comparative dye 3. The weight average molecular weight (Mw) of the comparative dye 3 was 18000, and the acid value was 1.81 mgKOH / g by titration using a 0.1N sodium hydroxide aqueous solution.

<Example 1>
1. Preparation of Resist Solution After mixing and dissolving components having the following composition, a resist solution for undercoat layer was prepared by filtering with a 0.45 μm nylon filter.
Composition of resist solution for undercoat layer: Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts 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) 40% PGMEA solution 30.51 parts Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA (Nippon Kayaku) 12.20 parts ・ Polymerization inhibitor: 0.0061 parts ・ Fluorosurfactant: F-475, 0.83 parts by DIC Corporation ・ Photopolymerization initiator: Trihalomethyltriazine -Based photopolymerization initiator (TAZ-107, manufactured by Midori Chemical Co., Ltd.) 0.586 parts

2. Preparation of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, an undercoat layer resist solution is applied onto the silicon wafer so as to have a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate was obtained.

3. Preparation of coloring composition 3-1. Preparation of blue pigment dispersion (preparation of pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion))
A pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion) was prepared as follows.
That is, C.I. I. Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as “PB15: 6”) 19.4 parts by mass (average primary particle diameter 55 nm), and dispersion resin BY-161 (manufactured by BYK) 2.95 parts by mass, 2. Mixing which mixed alkali-soluble resin J1 (copolymer of benzyl methacrylate / methacrylic acid, 30% PGMEA solution) 2.95 parts by mass (solution 9.93 parts by mass) and 165.3 parts by mass of PGMEA The liquid was mixed and dispersed for 3 hours by a beads mill (zirconia beads 0.3 mm diameter). Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained. The obtained C.I. I. With respect to Pigment Blue 15: 6 dispersion, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.

Alkali-soluble resin J1

3-2. Preparation of coloring composition The following components were mixed, dispersed and dissolved, and filtered through a 0.45 µm nylon filter to obtain a coloring composition.
Organic solvent (cyclohexanone): 17.12 parts Alkali-soluble resin 1 (J1 below): 1.23 parts (solid content 0.37 parts, solid content concentration 30%)
Alkali-soluble resin 2 (Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.23 part Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.975 part (Solid content concentration 12.3%): 24.57 parts pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion, PGMEA solution, solid concentration 12.8%): 51.40 parts polymerizable compound Z-1 (ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)): 1.96 parts, polymerization inhibitor (p-methoxyphenol): 0.0007 parts, fluorine Surfactant (DIC, F475, 1% PGMEA solution): 2.50 parts

4). Production of color filter (colored pattern) 4-1: Production of color filter using colored composition by photolithography method The colored composition prepared above is applied to the undercoat layer of the silicon wafer with an undercoat layer prepared above. To form a colored layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 1 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure dose of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.
The silicon wafer on which the colored pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is sprayed from the jet nozzle from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. The rinsing process was performed. Thereafter, it was spray-dried and post-baked on a hot plate at 200 ° C. for 300 seconds to obtain a colored pattern (color filter) having a film thickness of 1 μm on the silicon wafer.
As described above, a silicon wafer with a colored pattern having a structure in which a colored pattern (color filter) was provided on the undercoat layer of the silicon wafer with an undercoat layer was obtained.
Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation).
The development residue was evaluated using a colored pattern having an exposure amount of 1.0 μm in pattern size.

<< Evaluation of development residue >>
The outside of the colored pattern formation region (unexposed portion) on the silicon wafer was observed at a magnification of 30000 using a scanning electron microscope, and evaluated according to the following evaluation criteria.
A: No residue was observed outside the colored pattern formation region (unexposed area).
B: A small amount of residue was confirmed outside the colored pattern formation region (unexposed area), but was practically unproblematic.
C: A residue was confirmed outside the colored pattern formation region (unexposed portion). By changing the development condition from paddle development at 23 ° C. for 60 seconds to paddle development at 23 ° C. for 180 seconds, there was no practical problem.
D: Residue was remarkably confirmed outside the colored pattern formation region (unexposed portion).

<< Evaluation of color transfer >>
The absorbance of the colored pattern in each color filter was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance A).
A CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; transparent base material) was applied to the color pattern forming surface of the color filter so that the dry film thickness was 1 μm, and dried to form a transparent film. Thereafter, heat treatment was performed at 280 ° C. for 5 minutes.
After the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance B).
With respect to the value of absorbance B of the obtained transparent film, the ratio [%] to the value of absorbance A of the colored pattern measured before heating was calculated [the following (formula A)]. This was used as an index for evaluating the color transfer to adjacent pixels.
(Formula A) Color transfer (%) = (absorbance B / absorbance A) × 100
A: Less than 1% B: 1% or more and less than 3% C: 3% or more and less than 10% D: 10% or more

<< Light resistance evaluation >>
The colored photosensitive composition prepared above was applied to a glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film. And heat processing (prebaking) was performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.6 micrometer. Next, heating was performed at 200 ° C. for 5 minutes, and the coating film was cured to form a colored layer.
Using a light resistance tester (SX-75 manufactured by Suga Test Instruments Co., Ltd.), the glass substrate on which the colored layer is formed is black panel temperature 63 ° C., quartz inner filter, 275 nm cut outer filter, illuminance 75 mw / m ² (300 to 400 nm). The light resistance test was conducted for 10 hours under the condition of 50% humidity.
The color difference (ΔE * ab) before and after the light resistance test was measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). Based on the measured color difference (ΔE * ab), light resistance was evaluated according to the following evaluation criteria. It can be said that the smaller this value, the better the light resistance. The evaluation results are shown in the following table. A and B are levels at which there is no problem in actual use.

<Evaluation criteria>
A: ΔE * ab is 3 or less B: ΔE * ab is greater than 3 and less than 5 C: ΔE * ab is greater than 5 and less than 10 D: ΔE * ab is greater than 10

<< Evaluation of flatness >>
The coloring composition 1.0mL prepared above was apply | coated to the 4-inch silicon wafer using the spin coater (made by Mikasa Co., Ltd.), and the coating film was formed. And the heat treatment (prebaking) was performed for 120 seconds using a 100 degreeC hotplate so that the dry film thickness of the center part of this coating film might be 0.60 micrometer, and the colored layer was formed.
The thickness of the colored layer was measured using an optical film thickness meter (Filmetrics F20). It can be said that the smaller the difference between the thinnest part (center part) and the thickest part (peripheral part), the better. The evaluation results are shown in the following table. A and B are levels at which there is no problem in actual use.

<Evaluation criteria>
A: The difference in film thickness is 0.02 μm or less B: The difference in film thickness is greater than 0.02 μm and 0.05 μm or less C: The difference in film thickness is greater than 0.05 μm.

<Examples 2-52 and Comparative Examples 1-3>

In “3-2. Preparation of colored composition” in Example 1, except that the pigment dispersion, the dye multimer (dye), the photopolymerization initiator, the alkali-soluble resin, and the polymerizable compound were changed as shown in the following table. A colored composition was prepared in the same manner as in Example 1, and the development residue, color transfer, light resistance and flatness were evaluated in the same manner as in Example 1.
In Comparative Examples 1 to 3, the above-described comparative dyes S′-1 to S′-3 were used as the dye multimer.

From the said result, the coloring composition of Examples 1-52 was excellent in color transfer property, light resistance, and flatness. Furthermore, the development residue was extremely small and the developability was excellent.
On the other hand, Comparative Examples 1 to 3 were inferior in either color transfer or flatness.

<Examples 53 and 54>
The following components were mixed, dispersed and dissolved, and filtered through a 0.45 μm nylon filter to obtain a colored composition.
Next, the obtained colored composition was applied onto a 7.5 cm × 7.5 cm glass substrate using a spin coater so as to have a film thickness of 0.5 μm. Then, heating was performed for 5 minutes to cure the coating film to prepare a colored layer. The thickness of this colored layer was 0.5 μm.
Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied and prebaked at 90 ° C. for 1 minute to form a 0.8 μm-thick photoresist layer.
Subsequently, the photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.) with an exposure amount of 350 mJ / cm ² , and the temperature of the photoresist layer or the ambient temperature was 90 ° C. for 1 minute. The heat treatment was performed. Thereafter, development processing was performed with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, and further post-baking processing was performed at 110 ° C. for 1 minute to form a resist pattern. The resist pattern was formed with a side of 1.0 μm in consideration of etching conversion difference (pattern width reduction by etching).
Next, the glass substrate on which the photoresist layer is formed is attached to an 8-inch silicon wafer, and RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W using a dry etching apparatus (U-621, manufactured by Hitachi High-Technologies Corporation). The internal pressure of the chamber: 4.0 Pa, the substrate temperature: 50 ° C., the gas type and flow rate of the mixed gas are CF ₄ : 80 mL / min, O ₂ : 40 mL / min, Ar: 800 mL / min. As a result, the first stage etching process of 80 seconds was performed.
Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N ₂ : The second stage etching process was performed for 28 seconds at 500 mL / min, O ₂ : 50 mL / min, Ar: 500 mL / min (N ₂ / O ₂ / Ar = 10/1/10).
After performing dry etching under the above conditions, a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is used to perform stripping treatment at 50 ° C. for 120 seconds to remove the resist. Formed. Further, washing with pure water and spin drying were performed, and then a dehydration baking process was performed at 100 ° C. for 2 minutes. As a result, a color filter was obtained.
The resulting color filter was evaluated for color transfer, light resistance and flatness in the same manner as in Example 1.
<Composition of coloring composition>
Organic solvent (cyclohexanone): 17.12 parts Epoxy resin JER1031S (Mitsubishi Chemical Corporation, epoxy equivalent: 180-220 (g / eq.)): 4.395 parts Dye multimer cyclohexanone solution (solid (Concentration 12.3%): 24.57 parts • Pigment dispersion (see table below): 51.40 parts • Polymerization inhibitor (p-methoxyphenol): 0.0007 parts • Fluorosurfactant (DIC) F475, 1% PGMEA solution): 2.50 parts

  From the above results, the colored compositions of Examples 53 and 54 were excellent in color transfer, light resistance and flatness.

  Abbreviations of the compounds described in the table are as follows.

Photopolymerization initiator: Structure below

Alkali-soluble resin: the following structure

Polymerizable compound Z-1: Ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Z-2: Dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Z-3: Ethoxylation (4) Pentaerythritol tetraacrylate, SR494 (manufactured by Sartomer)
Z-4: Ethoxylation (3) Trimethylolpropane triacrylate, SR454 (manufactured by Sartomer)
Z-5: Ethoxylation (6) Trimethylolpropane triacrylate, SR499 (manufactured by Sartomer)
Z-6: KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.)
Z-7: Tris (2-hydroxyethyl) isocyanurate triacrylate, SR368 (manufactured by Sartomer)

Pigment Dispersion Pigment Dispersion P2 (CI Pigment Blue 15: 6 Dispersion:
In the preparation of the pigment dispersion P1, a pigment dispersion P2 was prepared by the same operation except that the following dispersion resin D1 was used instead of the dispersion resin BY-161.

Mw = 20000, x / y = 50/50 (mass ratio), n = 20, acid value = 100 mgKOH / g
Pigment dispersion P3 (CI Pigment Blue 15: 6 dispersion):
In preparing the pigment dispersion P1, a pigment dispersion P3 was prepared by the same operation except that the following dispersion resin D2 was used instead of the dispersion resin BY-161.

Mw = 20000, x / y = 15/85 (mass ratio), n = 20, acid value = 100 mgKOH / g
Pigment dispersion P4 (CI Pigment Violet 23 dispersion):
In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P4 was prepared in the same manner as the pigment dispersion P1 except that Pigment Violet 23 was used.
Pigment dispersion P5 (CI Pigment Red254 dispersion):
In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P5 was prepared in the same manner as the pigment dispersion P1 except that Pigment Red254 was used.
Pigment dispersion P6 (CI Pigment Green 58 dispersion):
In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P6 was prepared in the same manner as the pigment dispersion P1 except that Pigment Green 58 was used.
Pigment dispersion P7 (CI Pigment Yellow 139 dispersion):
In the preparation of the pigment dispersion P1, C.I. I. A pigment dispersion P7 was prepared in the same manner as the pigment dispersion P1, except that Pigment Yellow 139 was used.

Claims (18)

A coloring composition comprising a dye multimer represented by the general formula (1) and a polymerizable compound;
P- (Q) _n (1)
In general formula (1), P represents an n-valent linking group,
Q represents a polymer chain including a repeating unit having a dye structure, and the average value of the number of n repeating units having a dye structure is 2 or more,
n represents an integer of 3 to 10. The coloring composition according to claim 1, wherein the dye multimer is represented by the general formula (2);

In General Formula (2), A ¹ represents an n-valent linking group,
B ¹ represents a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—, and R represents a hydrogen atom Represents an alkyl group or an aryl group,
C ¹ represents a single bond or a divalent linking group,
S represents a sulfur atom,
Q represents a polymer chain including a repeating unit having a dye structure, and the average value of the number of n repeating units having a dye structure is 2 or more,
n represents an integer of 3 to 10. The A ¹ is a group consisting of one or a combination of two or more selected from an aliphatic hydrocarbon group, an aromatic ring group and a heterocyclic group which may have an oxygen atom in the main chain. The coloring composition as described in. The coloring composition according to any one of claims 1 to 3, wherein the dye multimer has a specific absorbance represented by the following formula (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm of 5 or more.
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye multimer in the solution expressed in mg / ml.   The coloring composition of any one of Claims 1-4 which contains the said pigment | dye multimer 1-50 mass% with respect to the total solid of the said coloring composition. The said pigment | dye multimer is obtained by radical-polymerizing the compound represented by General formula (3), and the compound which has a pigment | dye structure and a radically polymerizable group, The any one of Claims 1-5. The coloring composition as described in.
P ⁰ − (SH) _n (3)
In general formula (3), P ⁰ represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.   Furthermore, the coloring composition of any one of Claims 1-6 containing pigment | dyes other than the said pigment | dye multimer.   Furthermore, the coloring composition of any one of Claims 1-7 containing a photoinitiator.   The Q has a dye structure derived from a dye selected from a triarylmethane dye, a xanthene dye, an anthraquinone dye, a cyanine dye, a squarylium dye, a quinophthalone dye, a phthalocyanine dye, a subphthalocyanine dye, an azo dye, and a dipyrromethene dye. The coloring composition of any one of 1-8.   The colored composition according to claim 1, wherein Q has one or more selected from a repeating unit having an acid group and a repeating unit having a polymerizable group.   The coloring composition according to any one of claims 1 to 10, wherein Q is one selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins.   The color filter which uses the coloring composition of any one of Claims 1-11. Applying the colored composition according to any one of claims 1 to 11 on a support to form a colored composition layer;
Exposing the colored composition layer in a pattern;
Developing and removing unexposed portions of the colored composition layer exposed in a pattern to form a colored pattern; and
A pattern forming method including: Applying the colored composition according to any one of claims 1 to 11 on a support to form a colored composition layer, and curing to form a colored layer;
Forming a photoresist layer on the colored layer;
Patterning the photoresist layer by exposure and development to obtain a resist pattern; and
Forming a colored pattern by dry etching the colored layer using the resist pattern as an etching mask; and
A pattern forming method.   The manufacturing method of a color filter containing the pattern formation method of Claim 13 or 14.   A solid-state imaging device comprising the color filter according to claim 12 or a color filter obtained by the method for producing a color filter according to claim 15.   An image display device comprising the color filter according to claim 12 or a color filter obtained by the method for producing a color filter according to claim 15. A method for producing a dye multimer, comprising radical polymerization of a compound represented by the general formula (3) and a compound having a dye structure and a radical polymerizable group.
P ⁰ − (SH) _n (3)
In general formula (3), P ⁰ represents an n-valent linking group,
SH represents a thiol group,
n represents an integer of 3 to 10.