JP6147135B2 - Colored photosensitive resin composition, cured film, color filter, method for producing color filter, solid-state imaging device, and image display device - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition suitable for producing a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), and a colored region produced by the composition. The present invention relates to a color filter having a color filter, a solid-state imaging device having the color filter, and an image display device such as an organic LED liquid crystal display device.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal displays (LCD), especially color liquid crystal displays, has been increasing. The spread of organic EL displays is also awaited due to the demand for higher image quality. On the other hand, with the widespread use of digital cameras and camera-equipped mobile phones, demand for solid-state image sensors such as CCD image sensors has greatly increased.
Color filters are used as key devices for these displays and optical elements, and the demand for cost reduction is increasing along with the demand for higher image quality. Such a color filter is usually provided with a coloring pattern of three primary colors of red (R), green (G), and blue (B), and in a display device or an image sensor, light passing therethrough is divided into three primary colors. It plays a role to draw.

  As the colorant used in the color filter, a pigment is generally used. For example, the color compositions described in Patent Documents 1 to 3 are disclosed.

JP 2007-156395 A JP 2008-310000 A JP 2009-251481 A (Patent No. 5117913)

By the way, the crosstalk (mixture of light) is reduced by making the color filter thinner, but it is required to make the film thinner while maintaining the spectral shape, so it is required to greatly increase the pigment concentration in the solid content. It is done. For this reason, in the compositions described in Patent Documents 1 to 3, the content of components necessary for lithography is relatively reduced, and pattern formation tends to be difficult.
Thus, in order to ensure the content of the components necessary for lithography, it is an important issue to obtain a good pigment dispersion with a small amount of dispersant.

  The present invention solves such a problem, and it is possible to obtain a good dispersion with a small amount of a dispersing agent, and good lithography (resolution), pattern linearity, and the same color pixels between patterns. The present invention relates to a colored photosensitive resin composition excellent in stability and luminance unevenness, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the colored photosensitive resin composition.

As a result of detailed studies, the present inventors have found that the above-described problems can be solved by using a predetermined pigment and a predetermined dye derivative.
Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <15>.
<1> (A) a zinc halide phthalocyanine pigment, (B-1) a dye derivative represented by the following general formula (I) and / or (B-2) a dye derivative represented by the following general formula (II), Coloring containing (C) dispersant, (D) photopolymerization initiator, and (E) polymerizable compound, and the content of (C) dispersant is 20 to 40 parts by mass with respect to 100 parts by mass of pigment. Photosensitive resin composition.
(In General Formula (I), Dye represents an n-valent organic dye residue, X represents a single bond, —CONH—Y ² —, —SO ₂ NH—Y ² —, or —CH ₂ NHCOCH ₂ NH—Y ^2. — (Y ² represents an alkylene group or an arylene group which may have a substituent), Y ¹ represents —NH— or —O—, and Z represents a hydroxyl group when n represents 1. , An alkoxy group, a group represented by the following general formula (III), or -NH-X-Dye (X is the same as X in the general formula (I)), and n is an integer of 2 to 4. When it represents, it represents a hydroxyl group, an alkoxy group, or a group represented by the following general formula (III), R ¹ and R ² each represents an alkyl group which may have a substituent, R ¹ and R ² may form a heterocyclic ring containing bond to a nitrogen atom together .m is an integer of 1-6, For .n is 2 or more represents an integer of 1 to 4, a plurality of X, Y ^1, R ^1, and R ^2, respectively, may be the same or may be different.)
(In General Formula (III), Y ³ represents —NH— or —O—. R ¹ and R ² each represents an alkyl group which may have a substituent, and R ¹ and R ² are And may be bonded to form a heterocyclic ring containing a nitrogen atom (m represents an integer of 1 to 6).
(In General Formula (II), Dye represents an optionally substituted quinophthalone residue, and X ¹ represents —NR′SO ₂ —, —SO ₂ NR′—, —CONR′—, —CH ₂ NR′COCH ₂ NR′— or —NR′CO—, wherein X ² may have a substituent, an arylene group having 6 to 20 carbon atoms, or a substituent Represents a heteroaromatic group having 4 to 20 carbon atoms, and these groups are bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ — and —CO—. X ³ represents —NR′— or —O—, and R ′ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may have a substituent. It is B, and a group represented by the following general formula (1), a group represented by the following general formula _{(2), -O- (CH 2} ) n -R 8, -OR 9, -NR 10 R 11 , -Cl, represents -F and -X ³ -X ² -X ¹ group selected from -Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, R ^9, R ^10, R ¹¹ has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or a substituent. And an aryl group having 6 to 20 carbon atoms, and n represents an integer of 0 to 20. One of A and B is a group represented by the following general formula (1), the following general formula (2) a group represented _{by, -O- (CH 2) n-} R 8, is -OR ⁹ or -NR ¹⁰ R ^11, t is .t two or more represents an integer of 1 to 3 If a plurality of ^{X 1, X 2, X 3} , A, and B may be the same or different.)
(In General Formula (1), Y ¹ represents —NR′— or —O—, and Y ² has an alkylene group having 1 to 20 carbon atoms and a substituent which may have a substituent. An alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O—, — The divalent linking groups selected from SO ₂ — and —CO— may be bonded to each other, and R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, wherein R ¹ and R ² are each The C1-C20 alkyl group which may have a substituent, or the C2-C20 which may have a substituent .R ¹ and R ² representing an alkenyl group together, further nitrogen atom, heterocyclic structure which may be substituted include an oxygen atom or a sulfur atom may be formed.
In the general formula (2), Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR "-, -NR'-G- _{SO 2 -, - NR'-G} -SO 2 NR '' -, - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 - or -O-G-SO ₂ NR′-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An arylene group having 6 to 20 carbon atoms which may be substituted, and R ′ and R ″ are a hydrogen atom and an alkyl group having 1 to 20 carbon atoms and a substituent each optionally having a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ³ , R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 carbon atoms that may have a substituent. Represents an alkenyl group having 20 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, Or the C2-C20 alkenyl group which may have a substituent is represented. )
<2> The colored photosensitive resin composition according to <1>, further comprising a yellow pigment.
<3> The yellow pigment is C.I. I. Pigment yellow 150 and / or C.I. I. The colored photosensitive resin composition according to <2>, which is CI Pigment Yellow 185.
<4> (C) Any one of <1> to <3>, in which the dispersant is obtained by reacting a hydroxyl group of a vinyl polymer having a hydroxyl group at one end with a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. A colored photosensitive resin composition according to claim 1.
<5> The colored photosensitive resin composition according to any one of <1> to <4>, wherein in the general formula (I), Dye has a monoazo dye structure having a benzimidazolone skeleton.
<6> The colored photosensitive resin composition according to any one of <1> to <5>, wherein the quinophthalone residue is represented by the following general formula (II-1) in the general formula (II).
Formula (II-1)
(In General Formula (II-1), D and E may be formed together with a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring to which D and E are bonded, and having a substituent. Good aromatic or heterocyclic group, hydroxyl group, alkoxy group having 1 to 3 carbon atoms, carboxyl group or salt thereof, ester having 1 to 20 carbon atoms, amide having 1 to 20 carbon atoms, sulfone group or salt thereof, sulfamoyl Represents any group selected from a group, —NR′R ″ —, and a nitro group. In the formula, R ′ and R ″ each may have a hydrogen atom or a substituent and each have 1 carbon atom. Represents an alkyl group having ˜20, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, p is 0 to 4; Represents an integer, q is 4- In an integer calculated. * Represents the binding site to X ¹ in the general formula (II).)
<7> In the general formula (II), A and B represent a group represented by the general formula (1) or a group represented by the general formula (2), and are the same group, <1> The colored photosensitive resin composition in any one of-<6>.
<8> (A) The zinc halide phthalocyanine pigment is C.I. I. The colored photosensitive resin composition according to any one of <1> to <7>, which is CI Pigment Green 58.
<9> The colored photosensitive resin composition according to any one of <1> to <8>, wherein the total amount of the colorant is 40% by mass or more based on the total solid content in the composition.
<10> The colored photosensitive resin composition according to any one of <1> to <9>, which is used for forming a colored region of a color filter.
<11> A cured film obtained by curing the colored photosensitive resin composition according to any one of <1> to <10>.
<12> A step of forming a colored photosensitive resin composition layer by applying the colored photosensitive resin composition according to any one of <1> to <10> on a support, and a colored photosensitive resin composition layer A method for producing a color filter, which comprises a step of exposing the substrate to a pattern and a step of developing and removing unexposed portions to form a colored pattern.
<13> A step of applying the colored photosensitive resin composition according to any one of <1> to <10> on a support to form a colored photosensitive resin composition layer, and curing to form a colored layer. ,
Forming a photoresist layer on the colored layer;
A method for producing a color filter, comprising: a step of patterning a photoresist layer by exposure and development to obtain a resist pattern; and a step of dry etching a colored layer using the resist pattern as an etching mask.
<14> A color filter having the cured film according to <11> or a color filter manufactured by the method for manufacturing a color filter according to <12> or <13>.
<15> A solid-state imaging device or an image display device having the color filter according to <14>.

  According to the present invention, since a good dispersion can be obtained even if the content of the dispersant is small, excellent lithography (resolution), pattern linearity, stability between pixels of the same color in the pattern, and luminance unevenness are excellent. It has become possible to provide a colored photosensitive resin composition, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the colored photosensitive resin composition.

It is the figure which represented typically the criterion in evaluation of pattern linearity.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored photosensitive resin composition.

In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have 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 addition, “radiation” in the present specification 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 the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
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.

  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. .
The present invention has been made in view of the above situation, and an object thereof is to provide a coloring composition having excellent color characteristics.

<Colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is represented by (A) a zinc halide phthalocyanine pigment and (B-1) a general formula (I). And / or (B-2) a dye derivative represented by the general formula (II) (hereinafter sometimes collectively referred to as “(B) dye derivative”), (C) a dispersant, (D) A photopolymerization initiator and (E) a polymerizable compound are contained, and the content of the (C) dispersant is 20 to 40 parts by mass with respect to 100 parts by mass of the total amount of the pigment.

By using the composition of the present invention, a good dispersion can be obtained even if the content of the dispersant is reduced to 20 to 40 parts by mass with respect to 100 parts by mass of the pigment, so that good lithography (resolution) is obtained. In addition, pattern linearity, stability between pixels of the same color in the pattern, and luminance unevenness are improved. The reason why the effects of the present invention can be obtained is not clear, but depends on the fact that the planarity of the molecular structure of the halogenated zinc phthalocyanine used as the pigment is higher than that of non-halogenated phthalocyanine, copper phthalocyanine, etc. It is thought that there is. That is, it is considered that the pigment can be dispersed even with a small amount of the dispersant because the higher the planarity of the molecule is more easily adsorbed when the dispersant is dispersed by the interaction.
In addition, the (B) dye derivative used in the present invention has a triazine structure, and the triazine structure strongly adsorbs to a compound having high planarity. Therefore, the zinc halide phthalocyanine having high planarity depends on the dye derivative. It is strongly adsorbed. As a result, it is presumed that a very good dispersion with a low content of dispersant can be obtained.
Hereinafter, the composition of the present invention will be described in detail.

<< (A) Zinc Halide Phthalocyanine Pigment >>
The present invention includes (A) a zinc halide phthalocyanine pigment. In the halogenated zinc phthalocyanine pigment in the present invention, the substituents substituted on the phthalocyanine skeleton are only halogen atoms, and a total of at least two halogen atoms are bonded per phthalocyanine molecule (structure) in a maximum of 16 pieces. It is a structural pigment.
The halogen atom preferably contains at least one of a fluorine atom, a chlorine atom and a bromine atom, more preferably a chlorine atom and / or a bromine atom, and further preferably contains both a chlorine atom and a bromine atom.

As a halogenated zinc phthalocyanine pigment, the compound represented by the following general formula (F) is mentioned, for example.
(In the general formula (F), X ^{1 to} X ¹⁶ each represent a chlorine atom, a bromine atom or a hydrogen atom, and at least two of X ^{1 to} X ¹⁶ are a chlorine atom or a bromine atom.)

As the number of halogen atoms bonded in the molecule increases, the hue of the halogenated zinc phthalocyanine pigment changes from blue to green. In order for the halogenated zinc phthalocyanine pigment to become green, it is preferable that the halogen atom bonded to the molecule has 8 or more bromine atoms, and among them, having 12 or more bromine atoms is more yellowish. It is more preferable in terms of developing a high green color. It is preferable that more bromine atoms are contained than chlorine atoms in order to obtain a more yellowish green color.
Among these, those in which 8 or more of X ^{1 to} X ¹⁶ are substituted with bromine atoms exhibit a green color with high brightness, and are therefore suitable for use in green pixels (colored patterns) of color filters. The number of bromine atoms substituted is more preferably 10-14. Of X ^{1 to} X ¹⁶ , those taking hydrogen atoms are preferably 2 or less.

The zinc halide phthalocyanine pigment used in the present invention is preferably a halogenated zinc phthalocyanine having an average primary particle diameter of 0.01 to 0.30 μm. The average particle diameter of the primary particles of the pigment in the present invention is a value measured by the following method.
The average primary particle diameter in the present invention is the longer one of 100 primary particles of a zinc halide phthalocyanine pigment constituting an aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. It is the value which calculated | required each average value of the diameter (major axis) of this, and the shorter diameter (minor axis), and averaged it.

In the composition of the present invention, only one kind of zinc halide phthalocyanine pigment may be used, or a plurality of kinds may be used in combination. For example, in the general formula (F), a plurality of types of polyhalogenated zinc phthalocyanine pigments having a specific halogen atom composition, each having a different number of substitutions of halogen atoms selected from bromine atoms and chlorine atoms, are contained in a specific ratio. It may be a thing.
A preferred embodiment includes a combination of a polyhalogenated zinc phthalocyanine pigment containing 16 bromine atoms and a polyhalogenated zinc phthalocyanine pigment containing 15 bromine atoms and 1 chlorine atom. Moreover, as a ratio of both, it is preferable that it is the range of 80: 20-100: 0.

The average composition of the (A) zinc halide phthalocyanine pigment contained in the curable composition of the present invention is determined by mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography, Similarly, the mole% of each specific zinc halide phthalocyanine pigment contained in the pigment composition can be easily determined by analyzing the results of mass spectrometry.
The zinc halide phthalocyanine pigment that can be suitably used in the present invention can be produced by the methods described in JP-A-2007-320986 and JP-A-2008-19383.

  Examples of the halogenated zinc phthalocyanine pigment include C.I. I. And CI Pigment Green 58.

  The amount of the zinc halide phthalocyanine pigment in the composition of the present invention is preferably 20 to 100% by mass of the total pigment component, more preferably 30 to 90% by mass, and 40 to 80% by mass. Is more preferable.

-Other pigments-
The composition of the present invention may contain a pigment other than the halogenated zinc phthalocyanine pigment. Specifically, those described in Paragraph Nos. 0046 to 0052 of JP 2012-219106 A can be adopted, and the contents thereof are incorporated in the present specification. In the present invention, a yellow pigment is preferred. Other pigments may be used alone or in combination of two or more.

Examples of organic pigments include azo pigments, azomethine pigments, isoindoline pigments, and quinophthalone pigments. Of these, azo pigments and isoindoline pigments are preferred for the reason of dispersion stability. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199.
Among these, C.I. I. Pigment yellow 150 (azo pigment), C.I. I. Pigment Yellow 139,185 (isoindoline pigment) is preferable.

The other pigment used in the present invention preferably has one or two ring structures in the molecule constituting the other pigment. Here, the condensed ring has one ring structure as a whole.
Since pigments having one or two ring structures have a smaller intermolecular interaction direction than pigments having three or more ring structures, it is considered that the pigments can be easily released during dispersion (particulate formation). In addition, when the number of particles increases due to the dissolution of the pigment, adsorption to the halogenated zinc phthalocyanine pigment is likely to occur. Presumably effective in viscosity stability (inhibition of thickening). The pigment having one or two ring structures in the molecule constituting the pigment is preferably a yellow pigment. I. Pigment yellow 150, C.I. I. Pigment Yellow 185 is more preferable.

The composition of the present invention may contain (A) a known dye other than the pigment. 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, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc. Dyes can be used.
A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

The content of the pigment in the composition of the present invention is preferably 40% by mass or more based on the total amount of the phthalocyanine pigment and other pigments, excluding the solvent contained in the colored photosensitive resin composition. Preferably it is 45-70 mass%, More preferably, it is 50-65 mass%. The composition of the present invention may contain a dye within a range not departing from the gist of the present invention. When the dye is included, the total of the colorants (dye and pigment) is preferably within the above range.
Only one kind of pigment may be contained in the composition of the present invention, or two or more kinds thereof may be contained. When two or more types are included, the total amount is preferably within the above range.

<< (B) Dye derivative >>
The composition of the present invention comprises (B-1) a dye derivative represented by the general formula (I) and / or (B-2) a dye derivative represented by the general formula (II) as the (B) dye derivative. Including. Hereinafter, (B-1) the dye derivative represented by the general formula (I) and (B-2) the dye derivative represented by the general formula (II) will be described.

-(B-1) Dye derivative represented by general formula (I)-
(In General Formula (I), Dye represents an n-valent organic dye residue, X represents a single bond, —CONH—Y ² —, —SO ₂ NH—Y ² —, or —CH ₂ NHCOCH ₂ NH—Y ^2. — (Y ² represents an alkylene group or an arylene group which may have a substituent), Y ¹ represents —NH— or —O—, and Z represents a hydroxyl group when n represents 1. , An alkoxy group, a group represented by the following general formula (III), or -NH-X-Dye (X is the same as X in the general formula (I)), and n is an integer of 2 to 4. When it represents, it represents a hydroxyl group, an alkoxy group, or a group represented by the following general formula (III), R ¹ and R ² each represents an alkyl group which may have a substituent, R ¹ and R ² may form a heterocyclic ring containing bond to a nitrogen atom together .m is an integer of 1-6, For .n is 2 or more represents an integer of 1 to 4, a plurality of X, Y ^1, R ^1, and R ^2, respectively, may be the same or may be different.)
(In General Formula (III), Y ³ represents —NH— or —O—. R ¹ and R ² each represents an alkyl group which may have a substituent, and R ¹ and R ² are And may be bonded to form a heterocyclic ring containing a nitrogen atom (m represents an integer of 1 to 6).

Dye represents an n-valent organic dye residue. Examples of the organic dye residue include a chromogenic group in the pigment as described above, a similar structure, or a partial structure thereof. Specifically, a skeleton having an azo group, a skeleton having a urea structure, a skeleton having an amide structure, Examples include a structure containing one or more partial structures selected from a skeleton having a cyclic amide structure, an aromatic ring having a heteroatom-containing 5-membered ring, and an aromatic ring having a heteroatom-containing 6-membered ring, and Dye Is a substituent containing these organic dye residues.
The dye preferably has a pigment mother nucleus structure, or a pigment mother nucleus structure and an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring, and the amino group has a pigment mother nucleus structure, an aromatic ring It is bonded directly or via a linking group to any of the ring, nitrogen-containing aromatic ring, oxygen-containing aromatic ring and sulfur-containing aromatic ring. Specifically, quinoline residue, benzimidazolone residue, isoindoline residue, diketopyrrolopyrrole residue, azo residue, phthalocyanine residue, anthraquinone residue, quinacridone residue , Dioxazine residue, perinone residue, perylene residue, thioindigo residue, isoindoline residue, isoindolinone residue, quinophthalone residue, selenium residue, metal complex residue, etc. Is mentioned.

Specific examples of the organic dye residue represented by Dye include a copper phthalocyanine residue and the following organic dye residues. In the formula, * represents a binding site with X in the general formula (I).

  Among these, a monoazo dye having a benzimidazolone skeleton is preferable.

X represents a single bond, —CONH—Y ² —, —SO ₂ NH—Y ² — or —CH ₂ NHCOCH ₂ NH—Y ² —, and preferably a single bond.
Y ² represents an alkylene group or an arylene group which may have a substituent. As said alkylene group, a C1-C10 alkylene group is preferable, A C1-C6 alkylene group is more preferable, A C1-C3 alkylene group is more preferable. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. The alkylene group may have a substituent, and examples of the substituent include the groups described in the section of the substituent.
As said arylene group, a C6-C20 arylene group is preferable and a C6-C10 arylene group is more preferable. Specific examples include a phenylene group, a naphthylene group, and an anthracenylene group.
The alkylene group and the arylene group may have a substituent, and examples of the substituent include the groups described in the section of the substituent.

Y ¹ represents —NH— or —O—, preferably —NH—.

R ¹ and R ² each represents an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a heterocyclic ring containing a nitrogen atom.
As said alkyl group, a C1-C10 alkyl group is preferable and a C1-C6 alkyl group is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. The alkyl group may have a substituent, and examples of the substituent include the groups described in the section of the substituent.
R ¹ and R ² preferably represent an alkyl group which may have the same substituent.

m represents the integer of 1-6, 1-4 are preferable and 1-3 are more preferable.
n represents an integer of 1 to 4, preferably 1 to 3, and more preferably 1 or 2.

Z represents a hydroxyl group, an alkoxy group, a group represented by the following general formula (III), or —NH—X-Dye (where X is the same as X in the general formula (I)) when n represents 1. In the case where n represents an integer of 2 to 4, each represents a hydroxyl group, an alkoxy group, or a group represented by the following general formula (III).
When n represents 1, Z is preferably a group represented by the following general formula (III) or -NH-XQ, and more preferably a group represented by the following general formula (III).
When n represents an integer of 2 to 4, Z is preferably a group represented by the following general formula (III).

Formula (III)
(In General Formula (III), Y ³ represents —NH— or —O—. R ¹ and R ² each represents an alkyl group which may have a substituent, and R ¹ and R ² are And may be bonded to form a heterocyclic ring containing a nitrogen atom (m represents an integer of 1 to 6).

Y ³ represents —NH— or —O—, preferably —NH—. Y ³ preferably represents the same group as Y ¹ in formula (I).

R ¹ and R ² are in the formula (III), represents an optionally substituted alkyl group has the same meaning as R ¹ and R ² in formula (I), and preferred ranges are also the same . R ¹ and R ² in the general formula (III) preferably represent an alkyl group which may have the same substituent. Moreover, it is preferable that R < ¹ > and R < ² > in general formula (III) represent the alkyl group which may have the same substituent as R < ¹ > and R < ² > in general formula (I).

  m represents the integer of 1-6, 1-4 are preferable and 1-3 are more preferable. m preferably represents the same integer as m in formula (I).

  Specific examples of the basic dye derivative used in the present invention are shown below, but the present invention is not limited thereto.

-(B-2) Dye Derivative Represented by General Formula (II)-
Formula (II)
(In General Formula (II), Dye represents an optionally substituted quinophthalone residue, and X ¹ represents —NR′SO ₂ —, —SO ₂ NR′—, —CONR′—, —CH ₂ NR′COCH ₂ NR′— or —NR′CO—, wherein X ² may have a substituent, an arylene group having 6 to 20 carbon atoms, or a substituent Represents a heteroaromatic group having 4 to 20 carbon atoms, and these groups are bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ — and —CO—. X ³ represents —NR′— or —O—, and R ′ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may have a substituent. It is B, and a group represented by the following general formula (1), a group represented by the following general formula _{(2), -O- (CH 2} ) n -R 8, -OR 9, -NR 10 R 11 , -Cl, represents -F and -X ³ -X ² -X ¹ group selected from -Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, R ^9, R ^10, R ¹¹ has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or a substituent. And an aryl group having 6 to 20 carbon atoms, and n represents an integer of 0 to 20. One of A and B is a group represented by the following general formula (1), the following general formula (2) a group represented _{by, -O- (CH 2) n-} R 8, is -OR ⁹ or -NR ¹⁰ R ^11, t is .t two or more represents an integer of 1 to 3 If a plurality of ^{X 1, X 2, X 3} , A, and B may be the same or different.)
(In General Formula (1), Y ¹ represents —NR′— or —O—, and Y ² has an alkylene group having 1 to 20 carbon atoms and a substituent which may have a substituent. An alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O—, — The divalent linking groups selected from SO ₂ — and —CO— may be bonded to each other, and R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, wherein R ¹ and R ² are each The C1-C20 alkyl group which may have a substituent, or the C2-C20 which may have a substituent .R ¹ and R ² representing an alkenyl group together, further nitrogen atom, heterocyclic structure which may be substituted include an oxygen atom or a sulfur atom may be formed.
In the general formula (2), Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR "-, -NR'-G- _{SO 2 -, - NR'-G} -SO 2 NR '' -, - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 - or -O-G-SO ₂ NR′-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An arylene group having 6 to 20 carbon atoms which may be substituted, and R ′ and R ″ are a hydrogen atom and an alkyl group having 1 to 20 carbon atoms and a substituent each optionally having a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ³ , R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 carbon atoms that may have a substituent. Represents an alkenyl group having 20 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, Or the C2-C20 alkenyl group which may have a substituent is represented. )

In general formula (II), Dye represents the quinophthalone residue which may have a substituent. The quinophthalone residue is specifically represented by the following general formula (II-1).
Formula (II-1)
(In General Formula (II-1), D and E may be formed together with a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring to which D and E are bonded, and having a substituent. Good aromatic or heterocyclic group, hydroxyl group, alkoxy group having 1 to 3 carbon atoms, carboxyl group or salt thereof, ester having 1 to 20 carbon atoms, amide having 1 to 20 carbon atoms, sulfone group or salt thereof, sulfamoyl Represents any group selected from a group, —NR′R ″ —, and a nitro group. In the formula, R ′ and R ″ each may have a hydrogen atom or a substituent and each have 1 carbon atom. Represents an alkyl group having ˜20, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, p is 0 to 4; Represents an integer, q is 4- In an integer calculated. * Represents the binding site to X ¹ in the general formula (II).)

D and E are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring to which D and E are bonded, and an aromatic or heterocyclic group which may have a substituent, hydroxyl group Group, alkoxy group having 1 to 3 carbon atoms (for example, methoxy group, ethoxy group, propoxy group), carboxyl group or salt thereof, ester having 1 to 20 carbon atoms, amide having 1 to 20 carbon atoms, sulfone group or salt thereof , A sulfamoyl group, —NR′R ″ —, or a nitro group. R ′ and R ″ are each a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or a substituent. An aryl group having 6 to 20 carbon atoms which may have a group.
As a C1-C20 alkyl group, a C1-C10 alkyl group is preferable and a C1-C6 alkyl group is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group.
Examples of the aromatic ring group or the heterocyclic group include a phenyl group, a naphthyl group, a thiophene ring group, a pyridine ring group, and a pyrrole ring group.
The aromatic or heterocyclic group represented by D and E, the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ′ and R ″ are: It may have a substituent, and examples of the substituent include the groups described in the section of the substituent.
Among these, it is preferable that D and E are a hydrogen atom and a halogen atom.

  p represents an integer of 0 to 4, more preferably an integer of 1 to 4, and still more preferably 4. q represents an integer calculated by 4-p, specifically, an integer of 0 to 3 is preferable, 2-3 is more preferable, and 4 is more preferable.

The binding site with X ¹ in the general formula (II) is not particularly limited, but the 5th or 8th position of the quinoline skeleton in the quinophthalone residue is preferably a binding site, and the 8th position is a binding site. Is more preferable.

In formula (II), X ¹ _{is, -NR'SO 2 -, - SO 2} NR '-, - CONR' -, - CH 2 NR'COCH 2 NR'-, or -NR'CO- represent, -NR'SO ₂ - is preferable. When t is 2 or more, the plurality of X ¹ may be the same or different.

R ′ in X ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, Or the C6-C20 aryl group which may have a substituent is represented, and a hydrogen atom is preferable.
As said C1-C20 alkyl group, a C1-C10 alkyl group is preferable and a C1-C6 alkyl group is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group.
As said C2-C20 alkenyl group, a C2-C10 alkenyl group is preferable and a C2-C6 alkenyl group is more preferable. Specific examples include an ethynyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.
As said C6-C20 aryl group, a C6-C10 aryl group is preferable, and a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned specifically ,.
These may have a substituent, and examples of the substituent include the groups described in the section of the substituent.

In general formula (II), X ² is an arylene group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic ring having 4 to 20 carbon atoms which may have a substituent. Represents a group, and these groups may be bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ — or —CO— (R ′ represents the above X ^1). It is synonymous with R ′ in the middle, and the preferred range is also the same.). When t is 2 or more, the plurality of X ² may be the same or different.
The arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 10 carbon atoms, and specific examples include a phenylene group, a naphthylene group, and an anthracenylene group.
The heteroaromatic group having 4 to 20 carbon atoms is preferably a heteroaromatic group having 4 to 10 carbon atoms, and specific examples thereof include a thiophene ring group, a pyridine ring group, and a pyrrole ring group.
These may have a substituent, and examples of the substituent include the groups described in the section of the substituent.

X ³ represents —NR′— or —O—, preferably —NR′—. When t is 2 or more, the plurality of X ³ may be the same or different. R ′ has the same meaning as R ′ above, and the preferred range is also the same.

A and B are each a group represented by the following general formula (1) or the following general formula _{(2), -O- (CH 2} ) n -R 8, -OR 9, -NR 10 R 11, - Represents a group selected from Cl, -F or -X ³ -X ² -X ¹ -Dye, and one of A and B is a group represented by the following general formula (1) or (2); _{- (CH 2) n-R} 8, -OR 9, or -NR ¹⁰ R ^11. Among them, A and B are preferably groups represented by the following general formula (1) or the following general formula (2), and A and B are represented by the following general formula (1) or the following general formula (2). More preferably, A and B are the same group.

R ⁸ represents an optionally substituted nitrogen-containing heterocyclic residue, and specific examples thereof include a pyrrole ring residue and a pyridine ring residue.
R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkenyl having 2 to 20 carbon atoms which may have a substituent. Represents an aryl group having 6 to 20 carbon atoms which may have a group or a substituent. R ⁹ , R ¹⁰ and R ¹¹ have the same meaning as R ′ described above, and the preferred ranges are also the same.

General formula (1)
(In General Formula (1), Y ¹ represents —NR′— or —O—, and Y ² has an alkylene group having 2 to 20 carbon atoms and a substituent which may have a substituent. An alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O—, — The divalent linking groups selected from SO ₂ — and —CO— may be bonded to each other, and R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, wherein R ¹ and R ² are each independent. And an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 2 to 20 carbon atoms which may have a substituent. Represents a Kenyir group (R ¹ and R ² together form a further nitrogen atom, heterocyclic structure which may be substituted include an oxygen atom or a sulfur atom may be formed.)

Y ¹ represents —NR′— or —O—, preferably —NR′—. R ′ has the same meaning as R ′ above, and the preferred range is also the same.

Y ² may have a substituent, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms that may have a substituent, or a substituent. A good aryl group having 6 to 20 carbon atoms, and these groups are bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ —, and —CO—. (R ′ has the same meaning as R ′ above, and the preferred range is also the same).
The alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and further preferably an alkylene group having 1 to 3 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. The alkylene group may have a substituent, and examples of the substituent include the groups described in the section of the substituent.
The alkenylene group having 2 to 20 carbon atoms is preferably an alkenylene group having 1 to 10 carbon atoms, more preferably an alkenylene group having 1 to 6 carbon atoms, and further preferably an alkenylene group having 1 to 3 carbon atoms. Specific examples include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, and a hexynylene group. The alkenylene group may have a substituent, and examples of the substituent include the groups described in the section of the substituent.
The arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 20 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Specific examples include a phenylene group, a naphthylene group, and an anthracenylene group. The arylene group may have a substituent, and examples of the substituent include the groups described in the section of the substituent.

R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkenyl group having 2 to 20 carbon atoms which may have a substituent. (R ¹ and R ² may be combined to form an optionally substituted heterocyclic structure containing a nitrogen, oxygen or sulfur atom.
As said C1-C20 alkyl group, a C1-C10 alkyl group is preferable and a C1-C6 alkyl group is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group.
As said C2-C20 alkenyl group, a C2-C10 alkenyl group is preferable and a C2-C6 alkenyl group is more preferable. Specific examples include an ethynyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.
These groups may have a substituent, and examples of the substituent include the groups described in the section of the substituent. R ¹ and R ² preferably represent the same group.

General formula (2)
(In the general formula (2), Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR "-, -NR'-G. —SO ₂ —, —NR′—G—SO ₂ NR ″ —, —O—G—CO—, —O—G—CONR′—, —O—G—SO ₂ — or —O—G—SO ₂ represents NR′-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent or a substituent. An arylene group having 6 to 20 carbon atoms which may have, and R ′ and R ″ each represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms which may have a substituent; An alkenyl group having 2 to 20 carbon atoms which may have a group, or an aryl group having 6 to 20 carbon atoms which may have a substituent, R ³ , R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, Alternatively, it represents an aryl group having 6 to 20 carbon atoms which may have a substituent, and R ⁷ has an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may be present.)

Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, —NR′—, —NR′—G—CO—, NR′—G—CONR ″ —, —NR′—G—SO ₂ —, —NR ′. _{-G-SO 2 NR '' -} , - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 - or -O-G-SO ₂ NR'- represent single Bonding is preferred.
R ′ and R ″ are each a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, Or the C6-C20 aryl group which may have a substituent is represented. R ′ and R ″ are synonymous with R ′ in the general formula (1), and preferred ranges thereof are also the same.
G is an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. The number represents an arylene group having 6 to 20. G has the same meaning as Y ² in the general formula (1), and preferred ranges are also the same.

R ³ , R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 carbon atoms that may have a substituent. Represents an alkenyl group having ˜20 or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ³ , R ⁴ , R ⁵ , and R ⁶ have the same meaning as R ′ in the general formula (1), and the preferred ranges are also the same.

R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkenyl group having 2 to 20 carbon atoms which may have a substituent. R ⁷ has the same meaning as R ¹ in formula (1), and the preferred range is also the same.

  T in the general formula (II) represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

  Hereinafter, although the specific example of the pigment derivative represented by general formula (II) used for this invention is shown, this invention is not limited to these.

The content of the (B) pigment derivative in the present invention is preferably 0.5 parts by mass or more and 50 parts by mass or less, and preferably 1 part by mass or more and 25 parts by mass with respect to 100 parts by mass in total of the phthalocyanine pigment and other pigments. It is more preferable that the amount is not more than part by mass.
Only 1 type may be contained in the composition of this invention, and 2 or more types may be contained for the pigment derivative. When two or more types are included, the total amount is preferably within the above range.

<< (C) Dispersant >>
The composition of the present invention contains (C) a dispersant, and the content of the dispersant is 20 to 40 parts by mass with respect to 100 parts by mass of the pigment. In the present invention, a good dispersion can be obtained even if the content of the dispersing agent is small, so that excellent lithography (resolution), pattern linearity, stability between pixels of the same color in the pattern, and luminance unevenness are excellent. Become. In the present invention, the content of the (C) dispersant is preferably 22 to 38 parts by mass, and more preferably 25 to 35 parts by mass with respect to 100 parts by mass in total of the phthalocyanine pigment and other pigments.
Only 1 type of dispersing agent may be contained in the composition of this invention, and may be contained 2 or more types. When two or more types are included, the total amount is preferably within the above range.

Examples of the dispersant that can be used in the present invention include polymer dispersants [for example, 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, naphthalenesulfonic acid formalin condensate], and surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, and pigment derivatives. it can.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. 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 a polyester-based dispersant, specifically, JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, and JP-A-10-339949 Copolymers of macromonomer and nitrogen atom monomer described in JP-A-2004-37986, International Publication Pamphlet WO2010 / 110491, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A Grafts having partial skeletons and heterocyclic rings of organic dyes described in JP-A-2008-81732 Polymer, and a copolymer of a macromonomer and acid group-containing monomers described in JP 2010-106268 Publication. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 is a dispersibility of a pigment dispersion, a dispersion stability, and a colored photosensitive resin composition using the pigment dispersion. It is particularly preferable from the viewpoint of developability.

  As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), 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 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A-2-272 And polyester-based macromonomers described in Japanese Patent No. 009. Among these, the polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored photosensitive resin composition using the pigment dispersion. Particularly preferred is a polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009.

  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 dispersant that can be used in the present invention is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate) manufactured by BYK Chemie. , 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104 ” , P105 (high molecular weight unsaturated polycarboxylic acid), “EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester) manufactured by EFKA Amide), 5765 (high molecular weight polycarboxylate), 622 (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd. “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester) manufactured by Enomoto Kasei Co., Ltd. , DA-703-50, 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) "," Margen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative) ”manufactured by Nippon Lubrizol Corporation, 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan) manufactured by Nikko Chemical Monooleate), MYS-IEX (polyoxyethylene monostearate) ”, Kawano Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., organosiloxane polymer KP341, “W001: Cationic surfactant” manufactured by Shoji Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate Nonionic surfactants such as polyethylene glycol distearate and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA-47, EFKA-" manufactured by Morishita Sangyo Co., Ltd. 47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by San Nopco" Disperse Aid 6, Disperse Aid 8, Dispa Polymer dispersing agents such as Suede 15 and Disperse Aid 9100, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101 manufactured by ADEKA Corporation , P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like.

These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. 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 thereof include acidic cellulose derivatives, and (meth) acrylic acid copolymers are particularly preferable. 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.
It is also preferable to use a dispersant having the following structure.
(In the above, a is 2.0, b is 4.0, acid value is 10 mg KOH / g, and Mw 20000. Moreover, a and b each represent the number of partial structures represented in parentheses, and a + b = 6 is satisfied.)

  In the present invention, as the dispersant (C), it is particularly preferable to use a dispersant obtained by reacting a hydroxyl group of a vinyl polymer having a hydroxyl group at one end with a tricarboxylic anhydride or tetracarboxylic dianhydride. . Hereinafter, a dispersant formed by reacting a hydroxyl group of a vinyl polymer having a hydroxyl group at one end with a tricarboxylic anhydride or tetracarboxylic dianhydride will be described. By using such a compound, the adsorptive power between the (B) pigment derivative and the heterocyclic ring is improved, and the effects of the present invention are more effectively exhibited.

-Vinyl polymer having a hydroxyl group at one end-
The vinyl polymer having a hydroxyl group at one end is preferably a polymer represented by the following general formula (1). The polymer represented by the general formula (1) is a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer.
General formula (1)

(In General Formula (1), Y ² represents a polymerization termination group of a vinyl polymer, Z ² represents —OH or R ²⁸ (OH) ₂ , and R ²⁸ represents 3 having 1 to 18 carbon atoms. R ²¹ and R ²² each represent a hydrogen atom or a methyl group, one of R ²³ and R ²⁴ represents a hydrogen atom, the other represents an aromatic group, or — C (═O) —X ⁶ —R ²⁵ (wherein X ⁶ represents —O— or —N (R ²⁶ ) —, and R ²⁵ and R ²⁶ are each a hydrogen atom or a straight chain having 1 to 18 carbon atoms. A linear or branched alkyl group which may have an aromatic group as a substituent), X ⁴ represents a single bond, —O—R ²⁷ — or S—R ²⁷ —, and R ²⁷ Represents a linear or branched alkylene group having 1 to 18 carbon atoms, and n represents an integer of 2 to 50.)

Y ² represents a polymerization termination group of the vinyl polymer, and is any known polymerization termination group introduced when polymerization of a normal ethylenically unsaturated monomer is carried out by a usual method. For example, it can be a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Even if Y ² has any of these chemical structures, the dispersant of the present invention can exert its effect without being influenced by the polymerization termination group Y ² . Examples of the polymerization termination group include a carboxylic acid residue and an alcohol residue, and a carboxylic acid residue is preferable.

Z ² represents —OH or R ²⁸ (OH) ₂ , and —OH is preferred.
R ²⁸ represents a trivalent hydrocarbon group having 1 to 18 carbon atoms. R ²⁸ is preferably a C 1-18 trivalent hydrocarbon group, more preferably a C 1-10 trivalent hydrocarbon group, and even more preferably a C 1-6 trivalent hydrocarbon group. . As a trivalent hydrocarbon group, three hydrogen atoms are removed from a saturated hydrocarbon molecule having 1 to 18 carbon atoms such as methane, ethane, propane, 2-methylpropane, butane, cycloheptane, and cyclohexane. It is formed by removing three hydrogen atoms from an aromatic hydrocarbon molecule having 6 to 18 carbon atoms such as alkanetriyl group, benzene, naphthalene, anthracene, tetracene, biphenyl, acenaphthylene, phenalene, pyrene, and pyridine. And a group formed by removing three hydrogen atoms from benzene is preferable.
R ²¹ and R ²² each represent a hydrogen atom or a methyl group, preferably a hydrogen atom.

One of R ²³ and R ²⁴ represents a hydrogen atom, the other one is an aromatic group, or —C (═O) —X ⁶ —R ²⁵ (where X ⁶ represents —O— or —N (R ²⁶ )-represents an aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 14 carbon atoms, and further preferably an aromatic group having 6 to 10 carbon atoms. Specific examples include a phenyl group, a naphthyl group, and an anthracenyl group.
X ⁶ represents —O— or —N (R ²⁶ ) —, and R ²⁵ and R ²⁶ each represent a hydrogen atom or a linear or branched group having 1 to 18 carbon atoms, and has an aromatic group as a substituent. Represents an optionally substituted alkyl group. As a linear or branched alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. The aromatic group as a substituent of the alkyl group is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 14 carbon atoms, and further an aromatic group having 6 to 10 carbon atoms. preferable. Specifically, a phenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned.

X ⁴ represents a single bond, —O—R ²⁷ — or S—R ²⁷ —, and preferably S—R ²⁷ —.
R ²⁷ represents a linear or branched alkylene group having 1 to 18 carbon atoms. As a C1-C18 alkylene group, a C1-C10 alkylene group is preferable and a C1-C6 alkylene group is more preferable. Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, and a hexylene group.

  n represents an integer of 2 to 50, preferably an integer of 2 to 40, and more preferably an integer of 2 to 30.

The part of the repeating unit of the polymer represented by the general formula (1), that is, {-[C (R ²¹ ) (R ²³ ) -C (R ²² ) (R ²⁴ )] _n —} is mutually identical. (Homopolymer) made of a different material or (copolymer) made of a different material. In a preferred form of the polymer represented by the general formula (1), R ²¹ and R ²² are either a hydrogen atom, the other is a hydrogen atom or a methyl group, and R ²³ and R ²⁴ are either One is a hydrogen atom and the other is —C (═O) —O—R ²⁹ (R ²⁹ is a linear or branched alkyl group having 1 to 8 carbon atoms and has an aromatic group as a substituent. And —X ⁴ —Z ² is —S—CH ₂ CH ₂ —OH or —S—CH ₂ CH (OH) CH ₂ —OH.

  The method for producing the polymer represented by the general formula (1) can be referred to the descriptions in paragraphs 0044 to 0060 of Japanese Patent No. 5117913 (Japanese Patent Application Laid-Open No. 2009-251481), the contents of which are incorporated herein.

-Tricarboxylic anhydride or tetracarboxylic dianhydride-
Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid anhydride), etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride Products), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenylsulfo Such as tricarboxylic acid anhydride.

  When using a tricarboxylic acid anhydride, an aromatic tricarboxylic acid anhydride is preferable among the above.

  Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and polycyclic tetracarboxylic dianhydrides.

  Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,3-dimethyl. -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2, 3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4 , 5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, Cyclo [2,2,2] - such oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride can be mentioned.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3, 3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic dianhydride 2,2 ′, 3,3′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane Carboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3 , 4-Dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Propane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenyl Phosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, M-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, Examples thereof include 9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride.

  Examples of the polycyclic tetracarboxylic dianhydride include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2 , 3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride and the like.

  When tetracarboxylic dianhydride is used, aromatic tetracarboxylic dianhydride is preferable among the above.

  The tricarboxylic acid anhydride or tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure. These may be used alone or in combination. What is preferably used in the present invention is an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid dianhydride from the viewpoint of reducing the viscosity of the pigment dispersion or various inks. Furthermore, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2, 3,6,7-Naphthalenetetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester and trimellitic anhydride are preferred.

  Next, a process of reacting a hydroxyl group of a vinyl polymer having a hydroxyl group at one end with an acid anhydride group of an aromatic tricarboxylic acid anhydride will be described.

  When the number of moles of the hydroxyl group of the vinyl polymer having a hydroxyl group at one end is <H> and the number of moles of the carboxylic acid anhydride group of the aromatic tricarboxylic acid anhydride is <N>, the reaction ratio is 0.3 ≦ <H> / <N> ≦ 3 is preferable, and 0.5 ≦ <H> / <N> ≦ 2 is more preferable.

  A catalyst may be used for the reaction between the vinyl polymer having a hydroxyl group at one end and the aromatic tricarboxylic acid anhydride.

  As the catalyst, for example, a tertiary amine compound can be used, and triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene. , And 1,5-diazabicyclo- [4.3.0] -5-nonene.

  The reaction between the hydroxyl group of the vinyl polymer having a hydroxyl group at one end and the acid anhydride group of the aromatic tricarboxylic acid anhydride may be carried out without a solvent, or an appropriate dehydrated organic solvent may be used. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the product of the dispersant. The solvent to be used is not particularly limited, but ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like are used. Two or more of these solvents may be used in combination.

  The reaction temperature between the hydroxyl group of the vinyl polymer having a hydroxyl group at one end and the acid anhydride group of the aromatic tricarboxylic acid anhydride is preferably 50 ° C to 180 ° C, more preferably 60 ° C to 160 ° C. . When the reaction temperature is less than 50 ° C., the reaction rate is slow. When the reaction temperature exceeds 180 ° C., the acid anhydride that has reacted and opened the ring forms a cyclic anhydride again, which may make it difficult to complete the reaction.

<(D) Photopolymerization initiator>
The composition of this invention contains a photoinitiator from a viewpoint of the further sensitivity improvement.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound described later, 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 molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, 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 compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, triarylimidazole compounds, benzimidazole compounds, onium compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzimidazole compound is particularly preferable. The triarylimidazole compound may be a mixture with benzimidazole.
Specifically, examples of the trihalomethyltriazine compound include the following compounds. Note that Ph is a phenyl group.
Examples of the triarylimidazole compound and the benzimidazole compound include the following compounds.

A commercially available product can be used as the trihalomethyltriazine compound, for example, TAZ-107 (manufactured by Midori Chemical Co., Ltd.) can also be used.
In particular, when the composition of the present invention is used for the production of a color filter included in 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 polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. Considering these points, it is most preferable to use an oxime compound as the photopolymerization initiator (D) to form a fine pattern such as a solid-state imaging device.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Further, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1 -Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-cal Nilbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphine Oxides, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) And compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether) Benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators 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, IRGACURE-379, IRGACURE-OXE379 (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-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred 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 oxime compounds such as oxime derivatives that are suitably used as photopolymerization initiators in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) are also suitably used as commercial products.

  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, and ketoxime compounds described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are 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, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime compound that is a photopolymerization initiator is preferably a compound represented by the following general 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.

  The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group. , Isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoyl Methyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophena Sil group, 3-trifluoromethylphenacyl group, and 3-nitroph Nasir group can be exemplified.

  The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and specifically includes a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, and a 1-pyrenyl group. Group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, o- Cumenyl group, m-cumenyl group and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylyl Nyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracese Group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, Examples thereof include a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  As the acyl group, an acyl group having 2 to 20 carbon atoms is preferable, and specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl Group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group and 4-methoxybenzoyl group can be exemplified. .

  The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyl group. Examples thereof include an oxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylamino. Phenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group , 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyl Alkoxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

As the heterocyclic group, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom is preferable.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples thereof include a group, a pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, a morpholinyl group, and a thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and a trifluoromethylthiocarbonyl group. Can be illustrated.

  Specific examples of the arylthiocarbonyl group include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, and 4-dimethylaminophenylthiocarbonyl group. 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-triphenyl Fluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, And, and a 4-methoxyphenylthiocarbonyl group.

  In General Formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in General Formula (OX-2) described later, and preferred examples are also the same.

In the formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A in the formula (OX-1) is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, dodecyl) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. Group) substituted alkylene group, alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl) Group, a phenanthryl group, and a styryl group) are preferable.

In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (OX-1), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar in the formula (OX-1) and S adjacent thereto is a structure shown below. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following general formula (OX-2).

  In general formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0 to 0 It is an integer of 5. R, A and Ar in the general formula (OX-2) have the same meanings as R, A and Ar in the general formula (OX-1), and preferred examples thereof are also the same.

  In the general formula (OX-2), the monovalent substituent represented by X includes an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, and a heterocyclic ring. Group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, as X in the general formula (OX-2), an alkyl group is preferable from the viewpoints of solvent solubility and improvement of absorption efficiency in a long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  In the general formula (OX-2), examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the formula (OX-2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following general formula (OX-3) or (OX-4).

In general formula (OX-3) or (OX-4), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents 0. It is an integer of ~ 5. )
R, X, A, Ar, and n in the general formula (OX-3) or (OX-4) have the same meanings as R, X, A, Ar, and n in the general formula (OX-2), respectively. The preferred examples are also the same.

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

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 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. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

  You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

  The content of the photopolymerization initiator (D) in the composition of the present invention is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass with respect to the total solid content of the composition. It is 5 mass% or less, More preferably, it is 1 mass% or more and 3 mass% or less. Within this range, better sensitivity and pattern formability can be obtained.

<< (E) polymerizable compound >>
The composition of the present invention contains a polymerizable compound. In the present invention, known polymerizable compounds that can be cross-linked by radicals, acids, and heat can be used, and examples thereof include polymerizable compounds containing an ethylenically unsaturated bond, cyclic ether (epoxy, oxetane), methylol and the like. . The polymerizable compound is suitably selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, from the viewpoint of sensitivity. Among them, a polyfunctional polymerizable compound having 4 or more functional groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.

  Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and oligomers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, 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. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
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 at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylates obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as nurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A Urethane (meth) acrylates as described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Other preferable polymerizable compounds include a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated group. It is also possible to use a compound having two or more functions, a cardo resin.

  Moreover, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, paragraph numbers [0254] to [0257] of JP-A-2008-292970 are disclosed. Also suitable are the compounds described in.

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

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (═O) CH═CH ₂ or —OC. A group represented by (═O) C (CH ₃ ) ═CH ₂ is represented.
Specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.

  In addition, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof, and (meth) acrylated, It can be used as a polymerizable compound.

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

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferred, and in this ester, 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.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

Moreover, it is also a preferable aspect to contain a polyfunctional monomer having a caprolactone structure as the polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (Z-1) is preferable.

  In the general formula (Z-1), all six Rs 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. )

Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

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

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

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
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 the 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) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the oxygen atom side A form in which the terminal of X is bonded to X is preferred.

  The compounds represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (ii), 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 the general formula (Z-4) or the general formula (Z-5) is a conventionally known process, in which ethylene oxide or propylene oxide is opened to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by an addition reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative 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)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

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

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable compounds. By using the compounds, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
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), trimethylolpropane triacrylate (commercially available products are A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like. It is done.

  Examples of the cyclic ether (epoxy, oxetane) include those having an epoxy group such as JER-827, JER-828, JER-834, JER-1001, JER-1002, and JER-1003 as bisphenol A type epoxy resins. Bisphenol F As a type epoxy resin, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON830 EPICLON 835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and phenol novolac type epoxy resins such as JER-152, JER-154, JER- 157S70, JER-157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. As cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) , EO CN-1020 (manufactured by Nippon Kayaku Co., Ltd.), as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation) Celoxide 2021P, Celoxide 2081 Celoxide 2083, Celoxide 2085, EHPE-3150 (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol), EPOLEEAD PB 3600, PB 4700 (Above, manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-401 S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER -1031S (made by Japan Epoxy Resin Co., Ltd.) and the like. Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of the colored photosensitive resin composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, from the viewpoint of increasing the strength of the cured film formed from the colored photosensitive resin composition, those having three or more functional groups are preferable, and further, different functional groups / different polymerizable groups (for example, acrylic ester, methacrylate ester, styrene). It is also effective to adjust both sensitivity and strength by using a compound of a vinyl compound or a vinyl ether compound). Furthermore, in combination with tri- or more functional polymerizable compounds having different ethylene oxide chain lengths, the developability of the colored photosensitive resin composition can be adjusted, and an excellent pattern forming ability can be obtained. preferable.
In addition, the selection and selection of polymerizable compounds are also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiators, dispersions, alkali-soluble resins, etc.) contained in the colored photosensitive resin composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound in the composition of the present invention is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, and 7 to 15% by mass with respect to the total solid content in the colored photosensitive resin composition. % Is particularly preferred.

<< other ingredients >>
In addition to the components described above, the composition of the present invention is a range that does not impair the effects of the present invention, and (G) a resin having a polymerizable double bond in the side chain, an organic solvent, a crosslinking agent, etc. May be included.

-(G) Resin having a polymerizable double bond in the side chain-
In the present invention, if necessary, (G) a resin having a polymerizable double bond in the side chain may be contained. (G) By further containing a resin having a polymerizable double bond in the side chain, the composition of the present invention can be cured more effectively.

  (G) The resin having a polymerizable double bond in the side chain is not particularly limited as long as it has a polymerizable double bond in the side chain, but the polymerizable monomer having 2 to 6 hydroxyl groups (p) And a copolymer (a) with other polymerizable monomer (q), a resin obtained by reacting a functional group capable of reacting with a hydroxyl group and a compound (b) having an ethylenically unsaturated double bond Is preferred.

  (G) The polymerizable monomer (p) having 2 to 6 hydroxyl groups constituting the resin having a polymerizable double bond in the side chain has 2 to 6 hydroxyl groups and an ethylenically unsaturated double bond. For example, a monomer represented by the following general formula (1) can be used.

General formula (1)
(In the formula, R ¹ and R ⁴ each represent a hydrogen atom and an optionally substituted alkyl group having 1 to 5 carbon atoms, R ² represents an alkylene group having 1 to 4 carbon atoms, and R ³ represents 1 carbon atom. -4 represents an alkylene group or a single bond, and n represents an integer of 2 to 6.
Examples of the monomer represented by the general formula (1) include monoesters of polyhydric alcohols having an ethylenically unsaturated double bond, and glycerol mono (meth) acrylate is preferred.

  The other polymerizable monomer (q) is a polymerizable monomer copolymerizable with the polymerizable monomer (p) having 2 to 6 hydroxyl groups. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl ( (Meth) acrylates such as (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate N-vinylpyrrolidone; styrenes such as styrene and derivatives thereof, α-methylstyrene; acrylamides such as (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide, diacetone (meth) acrylamide; And other vinyl compounds such as (meth) acrylonitrile, ethylene, propylene, butylene, vinyl chloride, and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer. These monomers can be used individually by 1 type or in mixture of 2 or more types.

  The copolymerization ratio of the polymerizable monomer (p) having 2 to 6 hydroxyl groups and the other polymerizable monomer (q) is preferably 5 to 95% by weight: 95 to 5% by weight, 70% by weight: More preferably, it is 70 to 30% by weight. When the copolymerization ratio of the polymerizable monomer (p) is less than 5% by weight, the number of ethylenically unsaturated double bonds that can be introduced is small, the double bond equivalent value is large, and sufficient sensitivity can be obtained. Can not. When it exceeds 95% by weight, it is possible to introduce many ethylenically unsaturated double bonds, but since the ratio of the polymerizable monomer (q) is low, the dispersion stability, solubility, and chemical resistance are reduced. It becomes difficult to maintain physical properties such as these.

  Production of a copolymer (a) of a polymerizable monomer (p) having 2 to 6 hydroxyl groups and another polymerizable monomer (q) can be produced by a known method. No. 156930, paragraph 0013 can be referred to, the contents of which are incorporated herein.

(G) The resin having a polymerizable double bond in the side chain is obtained by reacting the copolymer (a) with a functional group capable of reacting with a hydroxyl group and a compound (b) having an ethylenically unsaturated double bond. Is obtained. Examples of the compound (b) having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond include an isocyanate group and a carboxyl group, and an isocyanate group is particularly preferred from the viewpoint of reactivity.
Specific examples of the compound having an isocyanate group and an ethylenically unsaturated double bond include 2-acryloylethyl isocyanate and 2-methacryloylethyl isocyanate. Specific examples of the compound having a carboxyl group and an ethylenically unsaturated double bond include acrylic acid, methacrylic acid, and maleic anhydride.

The amount of ethylenically unsaturated double bonds introduced into the copolymer (a) via a hydroxyl group is indicated by the “double bond equivalent” of the resulting resin. The double bond equivalent is defined by the following formula and is a measure of the amount of double bonds contained in the molecule. If the photosensitive resin has the same molecular weight, the smaller the double bond equivalent, the more The amount of introduced heavy bonds increases.
[Double bond equivalent] = [molecular weight of repeating structural unit] / [number of double bonds in repeating structural unit]
The double bond equivalent of the resin in the present invention is preferably 200 to 2,000, and more preferably 300 to 900. When the double bond equivalent of the resin is less than 200, the ratio of the polymerizable monomer (p) for introducing the ethylenically unsaturated double bond is increased, and a sufficient amount of the polymerizable monomer (for maintaining various properties) ( q) cannot be copolymerized. When it exceeds 2,000, sufficient sensitivity cannot be obtained because the number of ethylenically unsaturated double bonds is small.
The weight average molecular weight (Mw) of the (G) resin is preferably 2000 to 200000, more preferably 5000 to 50000, from the viewpoint of good dispersibility of the composition of the present invention.

  The reaction between the copolymer (a), the functional group capable of reacting with a hydroxyl group and the compound (b) having an ethylenically unsaturated double bond can be carried out by a known method, for example, JP-A-2005-156930. Reference can be made to the description of paragraph 0016 of the publication, the contents of which are incorporated herein.

When the composition of the present invention contains a resin having a polymerizable double bond in the side chain (G), the content of the resin having a polymerizable double bond in the side chain (G) is as follows: 10-100 mass% is preferable, More preferably, it is 20-90 mass%, More preferably, it is 30-80 mass%.
(G) 1 type of resin which has a polymerizable double bond in a side chain may be contained in the composition of this invention, and may be contained 2 or more types. When two or more types are included, the total amount is preferably within the above range.

-Alkali-soluble resin-
The composition of the present invention may further contain an alkali-soluble resin as a binder. In addition, the component contained in the composition of this invention as an dispersing agent component is not contained in alkali-soluble resin here.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility 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 a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. 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. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  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 linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. 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.

  The alkali-soluble resin may include a polymer (a) obtained by polymerizing a monomer component which essentially includes a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”). preferable.

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.

Thereby, the coloring composition of this invention can form the cured coating film which was very excellent also in transparency with heat resistance. In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. 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, (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-prope , 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-butyl) Cyclohexyl) -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.

  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. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include: 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 Industry Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting compound having polymerizable group, JP 2002-229207 A Resin obtained by basic treatment of a resin having 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-2003-335814 Etc. are preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, copolymerized 2-hydroxyethyl methacrylate, 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 macromonomer / Examples thereof include benzyl methacrylate / methacrylic acid copolymers, and particularly preferred are benzyl methacrylate / methacrylic acid copolymers.

As the alkali-soluble resin, paragraphs 0558 to 0571 of JP 2012-208494 A (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. 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 preferred to use a binder resin according to 030-0072. These contents are incorporated herein. More specifically, the following resins are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 mgKOH / g to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000. The method for measuring the molecular weight of the compound used in the present invention can be measured by gel permeation chromatography (GPC), and is defined as a polystyrene equivalent value by GPC measurement. For example, HLC-8220 (manufactured by Tosoh Corporation) is used, TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) is used as a column, and 10 mmol / L lithium bromide NMP (N— It can be determined by using a methylpyrrolidinone) solution.

When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin in the coloring composition is preferably 1% by mass to 15% by mass, more preferably based on the total solid content of the coloring composition. Is 2% by mass to 12% by mass, and particularly preferably 3% by mass to 10% by mass.
The composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

-Organic solvent-
The composition of the present invention may contain an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the colored photosensitive resin composition are satisfied. Is preferably selected in consideration of safety and safety. Moreover, when preparing the composition in this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons such as toluene And xylene are preferred.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, improvement of the coated surface, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the composition is preferably such that the total solid concentration of the composition is 5% by mass to 80% by mass from the viewpoint of applicability, and further 5% by mass to 60% by mass. Preferably, 10% by mass to 50% by mass is particularly preferable.

-Crosslinking agent-
It is also possible to supplement the composition of the present invention with a crosslinking agent to further increase the hardness of a cured film obtained by curing the composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.
The details of paragraphs 0134 to 0147 of JP-A No. 2004-295116 can be referred to for details such as specific examples of the crosslinking agent.
When the crosslinking agent is contained in the composition of the present invention, the blending amount of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the composition. preferable.
The composition of the present invention may contain only one type of cross-linking 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 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 composition.
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When a polymerization inhibitor is contained in the composition of the present invention, the addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition.
The composition of the present invention may contain only one 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 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.

In particular, since the composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and 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.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. 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 the 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, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  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.
Only one type of surfactant may be used, or two or more types may be combined.
When the composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.001% by mass with respect to the total mass of the composition. It is 005 mass%-1.0 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.

-Other additives-
Various additives, for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, and the like can be blended with the 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 composition of the present invention may 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 same publication.
Specifically, the following compounds are preferably used as the ultraviolet absorber.

--Organic carboxylic acid, organic carboxylic anhydride--
The composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

When the composition of the present invention contains an organic carboxylic acid and an organic carboxylic acid anhydride, the amount of these organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% in the total solid content. %, Preferably 0.03 to 5% by weight, more preferably 0.05 to 3% by weight.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved material of the composition while maintaining high pattern adhesion.

<Preparation method of colored photosensitive resin composition>
The composition of the present invention is prepared by mixing the aforementioned components.
In preparing the composition, the components constituting the composition may be combined at once, or may be sequentially combined 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 composition prepared as described above is preferably used after being filtered using a filter having a pore size of 0.01 μm to 3.0 μm, more preferably a pore size of about 0.05 μm to 0.5 μm. be able to.

  Since the composition of this invention can form the cured film excellent in heat resistance and a color characteristic, it is used suitably in order to form the coloring pattern (colored layer) of a color filter. In addition, the composition of the present invention is preferably used for forming a colored pattern such as a color filter used in a solid-state imaging device (for example, CCD, CMOS, etc.) or an image display device such as a liquid crystal display device (LCD). it can. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. In particular, a color filter for a solid-state imaging device such as a CCD and a CMOS can be suitably used as a production application.

<Curing film, pattern forming method, color filter, and color filter manufacturing method>
Next, the colored cured film, the pattern forming method, and the color filter in the present invention will be described in detail through the manufacturing method.

The pattern forming method of the present invention includes a colored composition layer forming step of forming a colored composition layer by applying the colored photosensitive composition of the present invention on a support, and exposing the colored composition layer in a pattern-like manner. It includes an exposure step and a pattern formation step of developing and removing unexposed portions to form a colored pattern.
The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.

  The support for forming a pattern by the pattern forming method of the present invention is not particularly limited as long as it is a support applicable to pattern formation in addition to a plate-like object such as a substrate.

  Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method.

The method for producing a color filter of the present invention applies the pattern forming method of the present invention, and includes a step of forming a colored pattern on a support using the pattern forming method of the present invention.
That is, the manufacturing method of the color filter of the present invention applies the pattern forming method of the present invention, and forms a colored composition layer by applying the colored photosensitive composition of the present invention onto a support. A physical layer forming step; an exposure step of exposing the colored composition layer in a pattern; and a pattern forming step of developing and removing an unexposed portion to form a colored pattern. Furthermore, you may provide the process (prebaking process) of baking a colored composition layer, and the process (post-baking process) of baking the developed coloring pattern as needed. Hereinafter, these steps may be collectively referred to as a pattern forming step.
The color filter of the present invention can be suitably obtained by the above production method.
Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.

  Each step in the pattern forming method of the present invention will be described in detail below through the color filter manufacturing method of the present invention.

  The manufacturing method of the color filter of this invention applies the pattern formation method of this invention, and includes forming a colored pattern on a board | substrate using the pattern formation method of this invention.

<Step of forming a colored photosensitive resin composition layer>
In the step of forming the colored photosensitive resin composition layer, the colored photosensitive resin composition layer forming step is formed by applying the composition of the present invention on the support.

As a support that can be used in this step, for example, a solid-state imaging in which an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). An element substrate can be used.
The colored pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light shielding film may be provided between the colored patterns in the solid-state image sensor or on the back surface of the substrate for the solid-state image sensor.
Further, 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 composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  The colored photosensitive resin 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, oven, or the like.

<< When pattern is formed by photolithography >>
-Exposure process-
In the exposure step, the colored photosensitive resin composition layer formed in the colored photosensitive resin composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using an exposure device such as a stepper, for example. Thereby, a cured film is obtained.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is more preferably 30mJ / cm ² ~1500mJ / cm ² is preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 being most preferred.

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2 μm to 0.8 μm.
It is preferable to set the film thickness to 1.0 μm or less because high resolution and high adhesion can be obtained.
In this step, a cured film having a thin film thickness of 0.7 μm or less can also be suitably formed. Although it exists, the coloring pattern excellent in developability, surface roughness suppression, and pattern shape can be obtained.

<<< Pattern formation process >>>
Next, by performing an alkali development treatment, the colored photosensitive resin composition layer in the light unirradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the photocured portion remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is conventionally 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further 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. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001% by mass to 10% by mass, An alkaline aqueous solution diluted with pure water so as to be preferably 0.01% by mass to 1% by mass is preferably used as the developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate 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.

Next, it is preferable to perform heat treatment (post-bake) after drying. If a multicolor coloring pattern is formed, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coated film after development is in the above-described condition be able to.

<< When pattern is formed by dry etching method >>
Dry etching can be performed by using an etching gas for the colored layer with the patterned photoresist layer as a mask. 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 a photoresist, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type radiation sensitive composition is used. As this positive type radiation sensitive composition, positive type photo sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A positive resist composition suitable for resist can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly 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 resolution, it is used for manufacturing integrated circuits such as ICs and LSIs. Examples of the quinonediazide compound include a naphthoquinonediazide compound. Examples of commercially available products include FHi622BC (manufactured by FUJIFILM Electronics Materials).

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, preferably 0.2 to 2.5 μm, and more preferably 0.3 to 2 μm. In addition, the application of the photoresist layer can be suitably performed using the above-described application method in the 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 dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the colored layer containing the colorant. Combinations of solvents and alkaline aqueous solutions 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 alkaline compounds 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. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water 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 provided in a checkered pattern 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). (4) The second stage etching is performed according to the etching time calculated in (2). 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) Overetching time is calculated with respect to the total time of (3) and (4), and overetching is performed.

The mixed gas used in the first stage etching step 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. The second etching step and the over-etching step may be performed by etching the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first etching process, and then damaging the support. From the viewpoint of avoidance, 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, the resist pattern formed on the first colored pattern only needs to be removed, and even when a deposit that is an etching product adheres to the side wall of the first colored pattern, The deposit may not be completely 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.

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

Further, when the composition according to the present invention is used, for example, clogging of a nozzle or a piping part of a coating apparatus discharge part, contamination due to adhesion, sedimentation, or drying of a colored composition or pigment in the coating machine may occur. . Therefore, in order to efficiently clean the contamination caused by the composition of the present invention, it is preferable to use the solvent related to the present composition 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 also be suitably used for cleaning and removing the composition according to the present invention.
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, and 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 with respect to contaminants, a surfactant related to the present composition may be added to the cleaning liquid.

Since the color filter of the present invention uses the composition of the present invention, exposure with excellent exposure margin can be achieved, and the formed colored pattern (colored pixel) has excellent pattern shape, and the surface of the pattern is rough and developed. Since the residue in the portion is suppressed, the color characteristics are excellent.
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.

In addition, as a film thickness of the coloring pattern (color pixel) in the color filter of this invention, 2.0 micrometers or less are preferable, 1.0 micrometer or less is more preferable, and 0.7 micrometer or less is further more preferable.
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 a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

A transfer electrode comprising a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. Having a light-shielding film made of tungsten or the like that is opened only in the light-receiving part of the photodiode, and having 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, It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.

[Image display device]
The color filter of the present invention can be used not only for the solid-state imaging device but also for an image display device such as a liquid crystal display device or an organic EL display device, and is particularly suitable for use in a liquid crystal display device. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image 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 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. In the color filter of the present invention, since a dye multimer excellent in hue is used, the color purity, light transmittance, etc. are good and the color pattern (pixel) is excellent in hue, so the resolution is high and the long-term durability is excellent. A COA type liquid crystal display device 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 materials, 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 of 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 LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

<Synthesis of Dispersant (C-1)>
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 80 parts of methyl methacrylate, 120 parts of ethyl acrylate, and 40 parts of methoxypropyl acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 4.4 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 times. Every 30 minutes, the reaction was continued for 12 hours at 80 ° C., and it was confirmed that 95% had reacted by solid content measurement. Next, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as catalyst were added at 120 ° C. The reaction was carried out for 2 hours at 80 ° C. for 5 hours, and it was confirmed by titration that 90% or more of the acid anhydride had been half-esterified. Sampling 2 g of resin solution, heating and drying at 180 ° C. for 20 minutes to measure the nonvolatile content, adding propylene glycol monomethyl ether acetate so that the nonvolatile content is 25% by weight, acid value per solid content of 44 mg KOH / g, A dispersant (C-1) having an aromatic carboxyl group having a number average molecular weight of 5200 was obtained.

<Synthesis of dispersant (C-2)>
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 160 parts of methyl methacrylate, 40 parts of ethyl acrylate, and 40 parts of methoxypropyl acetate were charged and replaced with nitrogen gas. Heat the inside of the reaction vessel to 80 ° C., add 2.2 parts of 3-mercapto-1,2-propanediol, then divide 0.2 part of 2,2′-azobisisobutyronitrile into 20 portions. Every 30 minutes, the reaction was continued for 12 hours at 80 ° C., and it was confirmed that 95% had reacted by solid content measurement. Next, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as catalyst were added at 120 ° C. The reaction was carried out for 2 hours at 80 ° C. for 5 hours, and it was confirmed by titration that 90% or more of the acid anhydride had been half-esterified. About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 25% by weight, and the acid value per solid content was 23 mgKOH / g, Dispersant (C-2) solution having an aromatic carboxyl group having a number average molecular weight of 11,000 was obtained.

<Synthesis of dispersant (C-3)>
The synthesis was carried out with reference to the description of paragraph number 0334 of JP-A-2007-277514.
Dispersant (C-3):
In the above, a is 2.0, b is 4.0, acid value is 10 mgKOH / g, and Mw20000.
Further, a and b each represent the number of partial structures represented in parentheses and satisfy a + b = 6.

<Synthesis of resin binder 1>
In a separable four-necked flask, a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer is charged with propylene glycol monomethyl ether acetate and heated to 100 ° C. while introducing nitrogen gas into the reaction vessel, At the same temperature, a mixture of 123.3 g of benzyl methacrylate, 25.8 g of methacrylic acid, and 10.0 g of azobisisobutyronitrile was dropped from the dropping tube over 1 hour to carry out a polymerization reaction.
After cooling to room temperature, about 3 g of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol acetate is added to the previously synthesized resin solution so that the nonvolatile content becomes 40% by mass. Thus, a solution of the resin binder 1 was obtained.

<Production of pigment dispersion composition>
A mixture having the following composition was uniformly stirred and mixed, and then mixed and dispersed for 3 hours by a bead mill to prepare Pigment Dispersion Composition 1.
Zinc halide phthalocyanine pigment (CI Pigment Green 58) 9.59 parts by weight Yellow pigment (CI Pigment Yellow 185) 4.11 parts by weight The following dye derivative (I-1) 1.37 parts by weight Dispersant (C-1) 4.93 parts by mass Propylene glycol monomethyl ether acetate (PGMEA) 80.0 parts by mass

Dye derivative (I-1):

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared by uniformly stirring and mixing a mixture having the following composition.
Pigment dispersion composition 1 65.7 parts by mass Resin binder 1 1.24 parts by mass (as 40% by mass resin solution)
Photopolymerization initiator (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF, IRGACURE OXE01))
1.26 parts by mass Ethylenically unsaturated compound (ethylene oxide modified product of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DPH-12E)) 2.34 parts by mass Fluorosurfactant (large (Nippon Ink Co., Ltd. MegaFuck F-781F)
0.02 parts by mass p-methoxyphenol 0.0003 parts by mass Propylene glycol monomethyl ether acetate (PGMEA)
29.44 parts by mass

  Photosensitive resin compositions 2 to 15 were prepared in the same manner as the photosensitive resin composition 1 except that the composition content was changed to the composition shown in the following table. In addition, derivative A, derivative (I-2), derivative (II-1), and derivative (II-2) used in photosensitive resin compositions 2 to 12 are represented by the following structural formulas.

Derivative A (Fuji Film Fine Chemicals Co., Ltd.):

Derivative (I-2):

Derivative (II-1):

Derivative (II-2):

<Evaluation>
<< residue >>
The colored photosensitive compositions of Examples and Comparative Examples obtained above were applied onto a silicon wafer with an undercoat layer using a spin coater so that the film thickness after application was 0.8 μm, and a hot plate at 100 ° C. Was subjected to heat treatment (pre-baking) for 120 seconds.
Next, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), the exposure amount is adjusted so that the pattern size becomes 1.4 μm square through a 1.4 μm square Bayer pattern mask at a wavelength of 365 nm. And exposed.
Thereafter, the glass wafer on which the exposed coating film was formed was subjected to paddle development for 60 seconds at 23 ° C. using a TMAH 0.3% aqueous solution. After that, rinse with a spin shower, rinse with pure water, heat treatment (post-bake) for 300 seconds using a 200 ° C. hot plate, and a monochromatic color with a 1.4 μm square Bayer pattern formed A filter was obtained.
Residues around the pattern were observed with respect to the obtained 1.4 μm square Bayer pattern using a length measurement SEM (S-4800, manufactured by Hitachi, Ltd.).
~ Criteria ~
5: No residue is observed.
4: A residue is slightly observed.
3: Although a residue is observed, it is a level which is satisfactory practically.
2: A residue is observed and is a level which cannot be used practically.
1: Residue is observed on the entire surface below the pattern.

<< Pattern linearity >>
The pattern substrate obtained above was observed from above using a length measurement SEM (S-4800, manufactured by Hitachi).
~ Criteria ~
5: One side of the pattern is a straight line as shown in FIG.
4: The corners of the pattern are slightly rounded as shown in FIG.
3: One side of the pattern is slightly rounded as shown in FIG.
2: The pattern is rounded as shown in FIG.
1: The pattern is round as shown in FIG.

<< Stability >>
The changes in viscosity after the above-obtained colored photosensitive compositions of Examples and Comparative Examples were aged at room temperature for 3 months were evaluated.
5: Viscosity change before and after aging is 3.0% or less.
4: The viscosity change before and after aging is more than 3.0% and 5.0% or less.
3: The viscosity change before and after aging is more than 5.0% and 10.0% or less.
2: The viscosity change before and after aging is more than 10.0% and 30.0% or less.
1: Viscosity change before and after aging exceeds 30.0%.

<< Luminance unevenness >>
The colored photosensitive compositions of Examples and Comparative Examples obtained above were applied on a glass substrate using a spin coater so that the film thickness after drying was 0.8 μm, and prebaked at 100 ° C. for 120 seconds. A colored coating film was obtained.
Each obtained colored coating film is placed between the observation lens and the light source of the optical microscope to irradiate light toward the observation lens, and the transmitted light state is an optical microscope in which a digital camera having a magnification of 1000 times is installed. Observed by. A digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels, and the surface of the coating film in a transmitted light state was photographed. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format.
In addition, imaging | photography of the coating film surface of a colored coating film was performed with respect to 20 area | regions selected arbitrarily. In addition, the digitally converted data was stored by digitizing the captured image as a density distribution of 256 gradations from 0 to 255 for each of the three primary colors of RGB.
Next, the stored digital image was divided into a grid shape so that one grid size corresponds to 0.5 μm square on the actual substrate, and the luminance in one section was averaged. In this example, since a 1.times.820,000 pixel digital camera took an image with a magnification of 1000 times, 0.5 μm on the actual substrate was 0.5 mm on the photographed image, and the image size on the display was 452 mm × 352 mm. Therefore, the total number of sections in one area was 636416.
For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A section having a difference from the average brightness of the adjacent section of 5% or more was recognized as a significant difference section, and the average total number of significant difference sections in all regions was calculated. The smaller the numerical value, the smaller the density difference between adjacent sections, the less the luminance unevenness, and the better the characteristics as a color filter.
~ Criteria ~
5: The number of significant difference sections is 2000 or less.
4: The number of significant difference divisions is 2001-3000.
3: The number of significant difference divisions is 3001-5000.
2: The number of significant difference divisions is 5001-10000.
1: The number of significant difference sections is 10001 or more.

In the above table, each symbol means the following compound.
PG58: zinc halide phthalocyanine pigment (CI Pigment Green 58)
PY139: Isoindoline yellow pigment (CI Pigment Yellow 139)
PY150: Nickel azo yellow pigment (CI Pigment Yellow 150)
PY185: Isoindoline yellow pigment (CI Pigment Yellow 185)
PG36: Copper halide phthalocyanine pigment (CI Pigment Green 36)
Unsubstituted Zn phthalocyanine pigment: non-halogenated zinc phthalocyanine pigment

From the results shown in the above table, when non-halogenated zinc phthalocyanine or halogenated copper phthalocyanine is used as the phthalocyanine pigment (Comparative Examples 1 to 5), pattern linearity, stability, and luminance unevenness are greatly inferior. all right. In addition, it was found that lithography, pattern linearity, stability, and luminance unevenness were greatly inferior when the pigment derivative or dispersant used in the present invention was not used (Comparative Examples 4 to 5).
On the other hand, for example, the photosensitive resin composition of the present invention shown in Examples includes (A) a zinc halide phthalocyanine pigment and (B) a dye derivative having a specific structure, which are essential components for the composition of the present invention. It can be seen that lithography, pattern linearity, stability, and luminance unevenness are greatly improved.

Claims (14)

(A) a halogenated zinc phthalocyanine pigment , (B-2) a dye derivative represented by the following general formula (II), (C) a dispersant, (D) a photopolymerization initiator , (E) a polymerizable compound and a yellow pigment Containing
The yellow pigment is C.I. I. Pigment yellow 150 and / or C.I. I. Pigment yellow 185,
(C) The coloring photosensitive resin composition whose content of a dispersing agent is 20-40 mass parts with respect to 100 mass parts of pigments.
(In General Formula (II), Dye represents an optionally substituted quinophthalone residue, and X ¹ represents —NR′SO ₂ —, —SO ₂ NR′—, —CONR′—, —CH ₂ NR′COCH ₂ NR′— or —NR′CO—, wherein X ² may have a substituent, an arylene group having 6 to 20 carbon atoms, or a substituent Represents a heteroaromatic group having 4 to 20 carbon atoms, and these groups are bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ — and —CO—. X ³ represents —NR′— or —O—, and R ′ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may have a substituent. It is B, and a group represented by the following general formula (1), a group represented by the following general formula _{(2), -O- (CH 2} ) n -R 8, -OR 9, -NR 10 R 11 , -Cl, represents -F and -X ³ -X ² -X ¹ group selected from -Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, R ^9, R ^10, R ¹¹ has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or a substituent. And an aryl group having 6 to 20 carbon atoms, and n represents an integer of 0 to 20. One of A and B is a group represented by the following general formula (1), the following general formula (2) a group represented _{by, -O- (CH 2) n-} R 8, is -OR ⁹ or -NR ¹⁰ R ^11, t is .t two or more represents an integer of 1 to 3 If a plurality of ^{X 1, X 2, X 3} , A, and B may be the same or different.)
(In General Formula (1), Y ¹ represents —NR′— or —O—, and Y ² has an alkylene group having 1 to 20 carbon atoms and a substituent which may have a substituent. An alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O—, — The divalent linking groups selected from SO ₂ — and —CO— may be bonded to each other, and R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, wherein R ¹ and R ² are each The C1-C20 alkyl group which may have a substituent, or the C2-C20 which may have a substituent .R ¹ and R ² representing an alkenyl group together, further nitrogen atom, heterocyclic structure which may be substituted include an oxygen atom or a sulfur atom may be formed.
In the general formula (2), Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR "-, -NR'-G- _{SO 2 -, - NR'-G} -SO 2 NR '' -, - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 - or -O-G-SO ₂ NR′-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An arylene group having 6 to 20 carbon atoms which may be substituted, and R ′ and R ″ are a hydrogen atom and an alkyl group having 1 to 20 carbon atoms and a substituent each optionally having a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ³ , R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 carbon atoms that may have a substituent. Represents an alkenyl group having 20 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, Or the C2-C20 alkenyl group which may have a substituent is represented. ) (A) a halogenated zinc phthalocyanine pigment, containing (B-2) dye derivative represented by the following general formula (II), (C) a dispersant, (D) a photopolymerization initiator and (E) a polymerizable compound A colored photosensitive resin composition comprising:
(C) The content of the dispersant is 20 to 40 parts by mass with respect to 100 parts by mass of the pigment,
The colored photosensitive resin composition whose total amount of a coloring agent is 40 mass% or more with respect to the total solid content in the colored photosensitive resin composition.
(In General Formula (II), Dye represents an optionally substituted quinophthalone residue, and X ¹ represents —NR′SO ₂ —, —SO ₂ NR′—, —CONR′—, —CH ₂ NR′COCH ₂ NR′— or —NR′CO—, wherein X ² may have a substituent, an arylene group having 6 to 20 carbon atoms, or a substituent Represents a heteroaromatic group having 4 to 20 carbon atoms, and these groups are bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ — and —CO—. X ³ represents —NR′— or —O—, and R ′ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may have a substituent. It is B, and a group represented by the following general formula (1), a group represented by the following general formula _{(2), -O- (CH 2} ) n -R 8, -OR 9, -NR 10 R 11 , -Cl, represents -F and -X ³ -X ² -X ¹ group selected from -Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, R ^9, R ^10, R ¹¹ has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or a substituent. And an aryl group having 6 to 20 carbon atoms, and n represents an integer of 0 to 20. One of A and B is a group represented by the following general formula (1), the following general formula (2) a group represented _{by, -O- (CH 2) n-} R 8, is -OR ⁹ or -NR ¹⁰ R ^11, t is .t two or more represents an integer of 1 to 3 If a plurality of ^{X 1, X 2, X 3} , A, and B may be the same or different.)
(In General Formula (1), Y ¹ represents —NR′— or —O—, and Y ² has an alkylene group having 1 to 20 carbon atoms and a substituent which may have a substituent. An alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O—, — The divalent linking groups selected from SO ₂ — and —CO— may be bonded to each other, and R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, wherein R ¹ and R ² are each The C1-C20 alkyl group which may have a substituent, or the C2-C20 which may have a substituent .R ¹ and R ² representing an alkenyl group together, further nitrogen atom, heterocyclic structure which may be substituted include an oxygen atom or a sulfur atom may be formed.
In the general formula (2), Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR "-, -NR'-G- _{SO 2 -, - NR'-G} -SO 2 NR '' -, - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 - or -O-G-SO ₂ NR′-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An arylene group having 6 to 20 carbon atoms which may be substituted, and R ′ and R ″ are a hydrogen atom and an alkyl group having 1 to 20 carbon atoms and a substituent each optionally having a substituent. Represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ³ , R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 carbon atoms that may have a substituent. Represents an alkenyl group having 20 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, Or the C2-C20 alkenyl group which may have a substituent is represented. ) The colored photosensitive resin composition according to claim 2 , further comprising a yellow pigment. The yellow pigment is C.I. I. Pigment yellow 150 and / or C.I. I. The colored photosensitive resin composition according to claim 3 , which is CI Pigment Yellow 185. (C) dispersing agent, obtained by reacting a vinyl polymer hydroxyl tricarboxylic acid anhydride or tetracarboxylic acid dianhydride having a hydroxyl group at one terminal, according to any one of claims 1-4 Colored photosensitive resin composition. The colored photosensitive resin composition according to any one of claims 1 to 5, wherein in the general formula (II), the quinophthalone residue is represented by the following general formula (II-1).
Formula (II-1)
(In General Formula (II-1), D and E may be formed together with a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring to which D and E are bonded, and having a substituent. Good aromatic or heterocyclic group, hydroxyl group, alkoxy group having 1 to 3 carbon atoms, carboxyl group or salt thereof, ester having 1 to 20 carbon atoms, amide having 1 to 20 carbon atoms, sulfone group or salt thereof, sulfamoyl Represents any group selected from a group, —NR′R ″ —, and a nitro group. In the formula, R ′ and R ″ each may have a hydrogen atom or a substituent and each have 1 carbon atom. Represents an alkyl group having ˜20, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, p is 0 to 4; Represents an integer, q is 4- In an integer calculated. * Represents the binding site to X ¹ in the general formula (II).)   In General Formula (II), A and B represent the group represented by General Formula (1) or the group represented by General Formula (2), and are the same group of Claims 1-6. The colored photosensitive resin composition of any one of Claims 1.   (A) A zinc halide phthalocyanine pigment is C.I. I. The colored photosensitive resin composition according to claim 1, which is CI Pigment Green 58. The colored photosensitive resin composition according to any one of claims 1 to 8 , which is used for forming a colored region of a color filter. Cured film obtained by curing the colored photosensitive resin composition according to any one of claims 1-9. Applying the colored photosensitive resin composition according to any one of claims 1 to 9 on a support to form a colored photosensitive resin composition layer, and patterning the colored photosensitive resin composition layer A method for producing a color filter, comprising: a step of exposing in a shape; and a step of developing and removing unexposed portions to form a colored pattern. Applying the colored photosensitive resin composition according to any one of claims 1 to 9 on a support to form a colored photosensitive resin composition layer, and curing to form a colored layer;
A step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask A method for producing a color filter. A color filter having the cured film according to claim 10 . A solid-state imaging device or an image display device having the color filter according to claim 13 .