WO2015029643A1

WO2015029643A1 - Coloring photosensitive resin composition, cured film, color filter, method for producing color filter, solid-state imaging element and image display device

Info

Publication number: WO2015029643A1
Application number: PCT/JP2014/069234
Authority: WO
Inventors: 和也尾田; 陽樹稲部
Original assignee: 富士フイルム株式会社
Priority date: 2013-08-28
Filing date: 2014-07-18
Publication date: 2015-03-05
Also published as: KR20160022900A; JP2015045736A; TW201508416A; TWI632426B; JP6147143B2; KR20170132339A; KR101943339B1

Abstract

Provided are: a coloring photosensitive resin composition which has small spectral variation and enables achievement of excellent resolution of a fine pattern; and a cured film, a color filter, a method for producing a color filter, a solid-state imaging element and an image display device, each of which utilizes the coloring photosensitive resin composition. This coloring photosensitive resin composition contains (A) a pigment, (B) another pigment, (C) a resin which has a weight average molecular weight of 38,000 or less and contains an acid group, (D) a pigment dispersant and (E) a pigment derivative. The pigment (A) is composed of at least one pigment that is selected from among red pigments and orange pigments, and the mass ratio of a red pigment relative to the pigment (A), namely (red pigment)/(pigment (A)) is 0.3 or more. The pigment (B) is composed of at least one pigment that is selected from among green pigments, blue pigments and black pigments, and the mass ratio of the pigment (B) relative to all the pigments contained in the composition, namely (pigment (B)/all pigments) is 0.005-0.25.

Description

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

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, the demand for solid-state imaging devices 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.

Patent Documents 1 and 2 describe red colored photosensitive resin compositions having a plurality of dye carriers (pigments), for example, as colored photosensitive resin compositions used in color filters.

JP 2010-61150 A (Patent No. 5210286) JP 2005-181384 A (Patent No. 4538220)

As in Patent Documents 1 and 2, in order to control and adjust red transmitted light and spectrum, a method using a plurality of dye carriers, that is, one or more of a red pigment, a green pigment, a blue pigment, and a black pigment A method of adding and mixing the above pigments is known.
However, it has been found that when a plurality of pigments are mixed with time, the added green pigment, blue pigment, and black pigment are aggregated and the spectrum is changed. Furthermore, when the pigment is aggregated, there is a problem that the resolution of the fine pattern is inferior.

The present invention solves such a problem, and even if it contains a plurality of pigments, the spectral variation of the spectrum is small, and the colored photosensitive resin composition is excellent in the resolution of fine patterns, and the colored photosensitive resin composition The present invention relates to a cured film, a color filter, a manufacturing method of a color filter, a solid-state imaging device, and an image display device using an object.

As a result of detailed studies, the present inventors have found that the above problem can be solved by using a predetermined resin having a weight average molecular weight of 38000 or less.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <17>.
<1> Colored photosensitivity containing (A) pigment, (B) pigment, and (C) a resin containing an acid group and having a weight average molecular weight of 38000 or less, (D) a pigment dispersant, and (E) a pigment derivative. (A) The pigment is at least one selected from a red pigment and an orange pigment, and (A) the mass ratio of the red pigment to the pigment (red pigment / (A) pigment) is It is 0.3 or more, and the (B) pigment comprises at least one selected from a green pigment, a blue pigment and a black pigment, and the mass ratio of the (B) pigment to the total pigment contained in the colored photosensitive resin composition A colored photosensitive resin composition, wherein ((B) pigment / total pigment) is 0.005 to 0.25.
<2> (D) a pigment dispersant is (D-1) a polymer (POH) having a hydroxyl group at at least one terminal or a polymer (PNH ₂ ) having a primary amino group at at least one terminal; A carboxylic acid-based dispersant obtained by reacting a tricarboxylic acid anhydride or a tetracarboxylic dianhydride; (D-2) a phosphoric acid-based dispersant represented by the following general formula (3); (D-3) At least one selected from a copolymer containing a structural unit represented by any one of the general formula (1) and the following general formula (2), and (D-4) a graft copolymer containing a nitrogen atom in the main chain The colored photosensitive resin composition according to <1>, which is a seed.

(In general formula (3), R ³ represents a polyester structure having a number average molecular weight of 400 to 30,000, and y represents 1 or 2. When y is 2, a plurality of R ³ may be the same. May be different.)

(In the general formulas (1) and (2), R ¹ to R ⁶ each represents a hydrogen atom or a monovalent organic group, and X ¹ and X ² represent —CO—, —C (= O) represents O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each represent a single bond or a divalent organic linking group, and A ¹ and A ² Each represents a monovalent organic group, m and n each represents an integer of 2 to 8, and p and q each represents an integer of 1 to 100.)
<3> (E) The pigment derivative is at least one of a pigment derivative represented by the general formula (I), a pigment derivative represented by the general formula (II), and a pigment derivative represented by the general formula (III) The colored photosensitive resin composition according to <1> or <2>.

(In the 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 optionally substituted alkylene group or arylene group), Y ¹ represents —NH— or —O—, and Z represents a hydroxyl group when n represents 1. Represents an alkoxy group, a group represented by the following general formula (I-1), or —NH—X-Dye (where X is as defined for X in the general formula (I)), and n is 2 to 4. In the case of representing an integer, each represents a hydroxyl group, an alkoxy group, or a group represented by the following general formula (I-1), R ¹ and R ² each represents an alkyl group which may have a substituent, optionally R ¹ and R ² are bonded to each other to form a heterocyclic ring containing a nitrogen atom .m is an integer of 1-6, If .n represents an integer of 1 to 4 is 2 or more, plural X, Y ^1, R ^1, and R ^2, respectively, may be the same or may be different.)

(In General Formula (I-1), 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 May be bonded to each other to form a heterocyclic ring containing a nitrogen atom, and m represents an integer of 1 to 6.

(In the 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 — or —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 (II-1), a group represented by the following general formula (II-2), -O- ( CH 2) n -R 8, -OR 9, - NR ¹⁰ R ¹¹ , —Cl, —F and —X ³ —X ² —X ¹ —Dye represent a group, R ⁸ represents an optionally substituted nitrogen-containing heterocyclic residue, R ⁹ , R ¹⁰ and R ¹¹ 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 Represents an aryl group having 6 to 20 carbon atoms which may have a substituent, and n represents an integer of 0 to 20. One of A and B is represented by the following general formula (II-1). is the group, the group represented by the following general formula (II-2), -O- ( CH 2) n-R 8, is -OR ⁹ or -NR ¹⁰ R ^11, t is 1 to 3 If .t represents an integer of 2 or more, a plurality of ^{^{^{X 1, X 2, X 3}}} , A, and B may be the same or different.)

(In General Formula (II-1), Y ¹ represents —NR′— or —O—, and Y ² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenylene group having 2 to 20 carbon atoms which may be substituted, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O— , —SO ₂ —, and —CO— may be bonded to each other through a divalent linking group, R ′ is a hydrogen atom, and may have a substituent and has 1 to 20 carbon atoms. R ¹ and R ² represent an alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. Each of the alkyl groups having 1 to 20 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent. .R ¹ and R ² representing the 0 alkenyl groups together, further nitrogen atom, heterocyclic structure which may be substituted include an oxygen atom or a sulfur atom may be formed.
In general formula (II-2), Z ¹ is a single bond connecting the triazine ring and the 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 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 substituent Represents an arylene group having 6 to 20 carbon atoms which may have a group, and R ′ and R ″ each represents a hydrogen atom and 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. 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. an alkenyl group having 1-20 or carbon atoms, which may have a substituent or an aryl group of 6 to 20, alkyl group of R ⁷ is - 1 carbon atoms, which may have a substituent group 20, Alternatively, it represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent. )
Formula (III)

(In the general formula (III), A represents a component capable of forming an azo pigment together with XY. X represents a single bond or a group selected from divalent linking groups in the following group A. Y represents a group represented by the following general formula (III-2).)
Group A:

(In the general formula (III-2), Z represents an alkylene group having 1 to 5 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms or a 5- or 6-membered saturated heterocyclic ring containing a nitrogen atom. A represents 1 or 2. * represents a binding site with X.)
<4> (A) The colored photosensitive resin composition according to any one of <1> to <3>, wherein the pigment contains an orange pigment.
<5> The colored photosensitive resin composition according to any one of <1> to <4>, wherein the total concentration of all pigments is 30% by mass or more based on the total solid content of the colored photosensitive resin composition. .
<6> (C) Any one of <1> to <5>, wherein the content of the resin containing an acid group and having a weight average molecular weight of 38000 or less is 25% by mass or less based on the total solid content of the composition A colored photosensitive resin composition according to claim 1.
<7> (A) The pigment is C.I. I. Pigment Red254, C.I. I. Pigment Red177 and C.I. I. The colored photosensitive resin composition according to any one of <1> to <6>, comprising at least one selected from Pigment Orange 71.
<8> The colored photosensitive resin composition according to any one of <1> to <7>, further comprising a polymerizable compound having four or more polymerizable groups.
<9> The colored photosensitive resin composition according to any one of <1> to <8>, further comprising a fluorine-based surfactant.
<10> The colored photosensitive resin composition according to any one of <1> to <9>, further comprising an oxime polymerization initiator.
<11> The colored photosensitive resin composition according to any one of <1> to <10>, further comprising a yellow pigment.
<12> The colored photosensitive resin composition according to any one of <1> to <11>, which is used for forming a colored region of a color filter.
<13> A cured film obtained by curing the colored photosensitive resin composition according to any one of <1> to <12>.
<14> a step of applying the colored photosensitive resin composition according to any one of <1> to <12> on a support to form a colored photosensitive resin composition layer; 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.
<15> A step of applying the colored photosensitive resin composition according to any one of <1> to <12> on a support to form a colored photosensitive resin composition layer and curing to form a colored layer Including 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 manufacturing a filter.
<16> A color filter having the cured film according to <13>, or a color filter manufactured by the method for manufacturing a color filter according to <14> or <15>.
<17> A solid-state imaging device or an image display device having the color filter according to <16>.

According to the present invention, a colored photosensitive resin composition excellent in spectral variability and fine pattern resolution, a cured film, a color filter, a method for producing a color filter, a solid using the colored photosensitive resin composition, a solid An image sensor and an image display device can be provided.

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. In the present specification, the total solid content means 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 specification, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, 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 this 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. .

<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 an (A) pigment, (B) pigment, and (C) an acid group having a weight average molecular weight of 38000 or less. A colored photosensitive resin composition comprising: (D) a pigment dispersant, and (E) a pigment derivative, wherein (A) the pigment comprises at least one selected from a red pigment and an orange pigment And (A) the mass ratio of the red pigment to the pigment (red pigment / (A) pigment) is 0.3 or more, and (B) the pigment is at least one selected from a green pigment, a blue pigment and a black pigment It consists of seeds, and the mass ratio of (B) pigment to all pigments contained in the composition ((B) pigment / total pigment) is 0.005 to 0.25.

The transmitted light can be controlled by adding at least one (B) pigment selected from a green pigment, a blue pigment and a black pigment to the (A) pigment containing the red pigment as an essential component. In such a case, the added (B) pigment was aggregated and the spectrum was changed. In this invention, it discovered that this subject could be solved by using resin whose weight average molecular weight is 38000 or less as (C) resin. Furthermore, it discovered that a litho residue could also be reduced. In particular, in the composition of this invention, it turned out that the one where the pigment density | concentration in solid content is high exists in the tendency for these effects to be exhibited effectively.
Hereinafter, the composition of the present invention will be described in detail.

<< (A) Pigment >>
The (A) pigment in the present invention comprises at least one selected from a red pigment and an orange pigment, and the mass ratio of the red pigment to the (A) pigment (red pigment / (A) pigment) is 0.3 or more. It is. That is, a red pigment may be included as an essential component, and an orange pigment may be further included. (A) The mass ratio of the red pigment to the pigment (red pigment / (A) pigment) is preferably 0.4 or more, and more preferably 0.44 or more. As the red pigment used in the present invention, various conventionally known red pigments can be used. The red pigment preferably has a high transmittance.

As red pigments, monoazo lake pigments, disazo pigments, naphthol pigments, naphthol lake pigments, pyrazolone pigments, BONA lake pigments, xanthene lake pigments, thioindigo pigments, perylene pigments, condensed azo pigments, anthraquinone lake pigments, benzimidazo Ron pigments, quinacridone pigments, diketopyrrolopyrrole pigments, azomethine metal complex pigments and the like. Specific examples include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 144, 146, 149, 168, 169, 177, 178, 180, 181, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, Red pigments such as 246, 254, 255, 264, and 272 can be used. In particular, from the viewpoint of the balance between hue and lightness, C.I. I. Pigment® Red 122, 177, 209, 224, 254 is preferably used, and at least one red pigment selected from the group consisting of C.I. I. Pigment Red254 and / or C.I. I. Pigment Red177 is more preferable.

Orange pigments include monoazo pigments, naphthol pigments, pyrazolone pigments, benzimidazolone pigments, disazo pigments, naphthol lake pigments, naphthalene sulfonic acid lake pigments, perinone pigments, quinacridone pigments, anthraquinone pigments, isoindolinone pigments, isoindoline. Pigments, azomethine metal complex pigments, diketopyrrolopyrrole pigments and the like. Specific examples include C.I. I. Pigment Orange 1, 2, 3, 5, 4, 24, 38, 74, 13, 34, 36, 60, 62, 64, 72, 15, 16, 17, 46, 19, 43, 48, 49, 51, 61 , 66, 68, 71, 73, 81 and the like can be used. I. Pigment® Orange 71 is preferable.

(A) The pigment is C.I. I. Pigment Red254, C.I. I. Pigment Red177 and C.I. I. It is preferable to include at least one selected from Pigment Orange 71.

The content of the pigment (A) in the composition of the present invention is preferably 10 to 70% by mass, more preferably based on all components (solid content) excluding the solvent contained in the colored photosensitive resin composition. It is 20 to 60% by mass, and more preferably 30 to 60% by mass.
(A) The pigment may be composed of one kind of pigment, or may be composed of two or more kinds of pigments. When two or more types are included, the total amount is preferably within the above range.

<< (B) Pigment >>
The (B) pigment used in the present invention comprises at least one selected from a green pigment, a blue pigment, and a black pigment.
As the green pigment, blue pigment, and black pigment used in the present invention, various conventionally known green pigments, blue pigments, and black pigments can be used. The green pigment, blue pigment, and black pigment preferably have high transmittance.

Examples of green pigments include phthalocyanine pigments, azomethine metal complex pigments, and the like. I. Pigment Green 1, 4, 7, 8, 36, 58, etc. can be used.

Examples of blue pigments include naphthol AS pigments, phthalocyanine pigments, dyed lake pigments, and anthraquinone pigments. Preferable examples include phthalocyanine pigments. I. Pigment Blue1, 25, 26, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 24: 1, 56, 60, etc. can be used.

Examples of black pigments include C.I. I. Pigment Black 6, 7, 12, 20, 31, 32, PO71, PO38, carbon black, carbon, titanium black, aniline black, anthraquinone black pigment, perylene black pigment, iron oxide, titanium oxide alone or in combination, Examples of the mixture include a combination of carbon and titanium black (the mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60). Among these, titanium black, carbon black, C.I. I. Pigment Black PO71 and PO38 are preferable.

The content of the pigment (B) in the composition of the present invention is preferably 0.1 to 60 parts by mass, more preferably 0.2 to 50 parts by mass, and still more preferably 100 parts by mass of the (A) pigment. Is 0.3 to 40 parts by mass.
(B) 1 type of pigments 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.

<< Other pigments and dyes >>
The composition of the present invention may contain other pigments and dyes without departing from the spirit of the present invention. Examples of other pigments include yellow pigments, brown pigments and purple pigments.

Examples of yellow pigments include monoazo pigments, monoazo lake pigments, disazo pigments, anthraquinone pigments, monoazopyrazolone pigments, condensed azo pigments, isoindoline pigments, benzimidazolone pigments, azomethine metal complex pigments, quinophthalone pigments, and quinoxaline pigments. Specifically, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Yellow pigments such as 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 can be used. In the present invention, C.I. I. Pigment Yellow 139 is particularly preferable.

The content of the yellow pigment in the composition of the present invention is preferably 0 to 60 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 20 to 40 parts by mass with respect to 100 parts by mass of the pigment (A). It is.
Only one kind of yellow 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.

In addition, as other pigments used in the present invention, for example, those described in paragraph No. 0053 of JP2013-068814A can be employed. These other pigments are preferably 1% by mass or less of the total pigments. Moreover, the dye may be included in the range which does not deviate from the meaning of this invention.

When used for a color filter, the primary particle size of the pigment used in the present invention is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. preferable. The primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm. In the present invention, a particularly good effect can be exhibited in combination with a pigment having a primary particle size in the range of 5 to 35 nm.
The primary particle size of the pigment can be measured by a known method such as an electron microscope.

<< Pigment ratio >>
In the composition of the present invention, the mass ratio of the (B) pigment to the total pigment contained in the composition ((B) pigment / total pigment) is 0.005 to 0.25, and 0.005 to 0.00. 2, more preferably 0.005 to 0.1, and still more preferably 0.005 to 0.05. (B) By adjusting the pigment concentration so as to be within the above range, aggregation of the pigment can be suppressed and the spectrum can be prevented from fluctuating.
Here, the term “all pigments” is intended to include other pigments such as (A) pigments, (B) pigments, and yellow pigments. In the present invention, the total of (A) pigment and (B) pigment preferably occupies 60% by mass or more of the total pigment, and the total of (A) pigment, (B) pigment and yellow pigment is 90% by mass of the total pigment. It is more preferable to occupy% or more.

In the composition of the present invention, the concentration of all pigments is preferably 30% by mass or more, more preferably 35% by mass or more, and 40% by mass or more with respect to the total solid content of the composition. More preferably. Although there is no restriction | limiting in particular about an upper limit, For example, it is 55 mass% or less. By adjusting the pigment concentration to be within the above range, the aggregation of the pigment can be suppressed, and the spectral fluctuation can be more effectively suppressed.

<< (C) resin containing acid groups and having a weight average molecular weight of 38000 or less >>
The composition of the present invention comprises (C) a resin containing an acid group and having a weight average molecular weight of 38000 or less (hereinafter also referred to as (C) resin). (C) By having resin, aggregation of a pigment can be suppressed and it can suppress that spectroscopy changes. It is also possible to reduce litho residue.

The (C) resin that can be used in the composition of the present invention is a linear organic polymer, and is a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as the main chain). ) Having at least one group that promotes alkali solubility in (C) resin. 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 acid group (group that promotes alkali solubility) contained in the resin (C) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, but it is soluble in an organic solvent and weakly alkaline. Those that can be developed with an aqueous solution are preferred, and (meth) acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.

(C) In order to introduce an acid group into the resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter also referred to as “monomer for introducing an acid group”) May be polymerized as a monomer component. Examples of the monomer that can give an acid group after polymerization include, for example, 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 (meth). And 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 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.

(C) For the production of the 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, and the like when the (C) resin is produced by the radical polymerization method can be easily set by those skilled in the art. It can also be determined.

(C) As the linear organic high molecular polymer used as the 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. Add acid anhydrides to polymers, maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, acidic cellulose derivatives with carboxylic acids in the side chain, and polymers with hydroxyl groups Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the (C) 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.

(C) The resin contains a polymer (a) obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”). Is also 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 colored photosensitive resin composition of this invention can form the cured coating film which was extremely excellent also in heat resistance and transparency. In the general formula (ED) representing 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 and 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl and 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-pro Noate, 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) Dicyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-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.

In addition to the above, it is preferable to include an ethylenically unsaturated monomer (a) represented by the following formula (X) as a monomer to be copolymerized with the (C) resin.
Formula (X)

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

In the above formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R ₃ may contain a benzene ring. When the carbon number of the alkyl group of R ₃ is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment. However, when the carbon number exceeds 10, The steric hindrance effect becomes high and shows a tendency to prevent even the adsorption / orientation of the benzene ring to the pigment. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₃ becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely reduced. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

Examples of the ethylenically unsaturated monomer (a) include phenol ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, and nonylphenol EO modified (meth). Examples thereof include acrylate, PO-modified (meth) acrylate of nonylphenol, and the like. Among these compounds, EO or PO-modified (meth) acrylate of paracumylphenol is not only effective for the π-electron of the benzene ring, but also its steric effect, which is better for coloring materials such as pigments. Since the adsorption / orientation plane can be formed, the dispersion effect is higher.

Further, in the present invention, a compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond in a copolymer of a polymerizable monomer having 2 to 6 hydroxyl groups and another polymerizable monomer A resin obtained by reacting is preferably used. The polymerizable monomer (a1) having 2 or more and 6 or less hydroxyl groups is preferably a compound having 2 or more and 6 or less hydroxyl groups and an ethylenically unsaturated double bond, for example, the following general formula (Y) The monomer shown by can be used.

General formula (Y)
CH ₂ R ₁ ═C (OH) —COO—R ₂ (CHR ₃ ) _n R ₄
(Wherein R ₁ and R ₄ each independently represents a hydrogen atom or 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 a carbon atom) Represents an alkylene group of 1 to 4 or a direct bond, and n represents an integer of 2 to 6.
Examples of the monomer represented by the general formula (Y) include monoesters of polyhydric alcohols having an ethylenically unsaturated double bond, and glycerol mono (meth) acrylate is preferred.

The other polymerizable monomer (a2) constituting such a copolymer is a polymerizable monomer copolymerizable with the polymerizable monomer (a1) having 2 to 6 hydroxyl groups, and the above-described polymerizable monomer. And monomers. These polymerizable monomers can be used individually by 1 type or in mixture of 2 or more types.

Further, in order to improve the crosslinking efficiency of the colored photosensitive resin composition in the present invention, (C) resin having a polymerizable group may be used. As the (C) resin having a polymerizable group, a (C) 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-described polymer containing a polymerizable group include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co.Ltd.), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. As the (C) 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 Containing urethane-modified polymerizable double bond-containing acrylic resin obtained by reaction with carboxylic acid, unsaturated group-containing acrylic resin containing carboxyl group-containing acrylic resin and compound having both epoxy group and polymerizable double bond in the molecule Acrylic resin, acid pendant epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting polymerizable double bond, OH group-containing acrylic resin and isocyanate A resin obtained by reacting a compound having a polymerizable group with JP-A-2002-229207 And resins obtained by subjecting a resin having a side chain with 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. Is preferred.

(C) Resin is particularly preferably a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers. In addition, copolymers of 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 resin (C), paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to. The contents are incorporated herein.
Further, the copolymer (B) described in paragraphs 0029 to 0063 described in JP2012-32767A and the resin (C) used in the examples, paragraph number 0088 of JP2012-208474A. To 0098 and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A, the binder resin used in the examples, and JP2013 No. 024934, paragraphs 0132 to 0143, and binder resins used in Examples, Japanese Unexamined Patent Publication No. 2011-242752, paragraphs 0092 to 0098 and binder resins used in Examples, Paragraph No. 0030 of JP2012-032770A It preferred to use a binder resin according to 0072. These contents are incorporated herein. More specifically, the following resins are preferable.

(C) The acid value of the resin is preferably 10 to 200 mgKOH / g, more preferably 20 to 180 mgKOH / g, and even more preferably 30 to 160 mgKOH / g.
The weight average molecular weight (Mw) of the (C) resin is 38000 or less, preferably 30,000 or less, more preferably 25,000, and most preferably 21,000. Although there is no restriction | limiting in particular about a minimum, 2000 or more are preferable and 8000 or more are more preferable.

(C) The amount of the ethylenically unsaturated double bond contained in the resin is indicated by “ethylenically unsaturated double bond equivalent”. 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 resin has the same molecular weight, the smaller the double bond equivalent value, The amount of introduction increases.
[Ethylenically unsaturated double bond equivalent] = [Molecular weight of repeating structural unit] / [Number of ethylenically unsaturated double bonds in repeating structural unit]
The ethylenically unsaturated double bond equivalent of the resin in the present invention is preferably 200 to 2,000, more preferably 300 to 1,000.

The content of the resin (C) in the composition of the present invention is preferably 25% by mass or less, more preferably 1 to 20% by mass, and further preferably 1 to 15% by mass with respect to the total solid content of the composition. It is particularly preferably 1 to 10% by mass.
The composition of this invention may contain only 1 type (C) resin, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

The composition of the present invention may contain a resin having an acid group having a weight average molecular weight exceeding 38000 within a range not departing from the gist of the present invention. It is preferable that the compounding quantity of such resin is 5 mass% or less of the compounding quantity of (C) resin.

<< (D) Pigment Dispersant >>
The composition of the present invention contains (D) a pigment dispersant (hereinafter, also simply referred to as “dispersant”). As the dispersant that can be used in the present invention, known dispersants can be widely used. For example, the description in paragraph numbers 0049 to 0055 of JP2013-077009A can be referred to, and the contents thereof are incorporated in the present specification.

In the present invention, (D) as a pigment dispersant, (D-1) a polymer having a hydroxyl group at one end (POH) or a polymer having a primary amino group at one end (PNH ₂ ) and a tricarboxylic acid anhydride or A compound obtained by reacting with tetracarboxylic dianhydride, (D-2) a copolymer containing a structural unit represented by any one of the following general formula (1) and the following general formula (2); D-3) at least selected from a compound containing a phosphate ester represented by the following general formula (3), and (D-4) a compound containing a nitrogen atom in the main chain represented by the following general formula (4) One type is preferably used. By using such a compound, the effects of the present invention are more effectively exhibited. Hereinafter, (D-1) to (D-4) will be described.

-(D-1) a polymer having at least one terminal hydroxyl group (POH) or a polymer having at least one terminal primary amino group (PNH ₂ ) and a tricarboxylic acid anhydride or tetracarboxylic acid dianhydride; Carboxylic acid-based dispersant made by reacting
The composition of the present invention comprises (D-1) a polymer (POH) having a hydroxyl group at at least one terminal or a polymer (PNH ₂ ) having a primary amino group at at least one terminal, and a tricarboxylic acid anhydride. Or it is preferable to have a carboxylic acid type | system | group dispersing agent formed by making a tetracarboxylic dianhydride react.

Carboxylic acid dispersants include a polymer having a hydroxyl group at at least one terminal (POH) or a polymer having a primary amino group at at least one terminal (PNH ₂ ), a tricarboxylic acid anhydride or a tetracarboxylic acid dicarboxylic acid. It can be obtained by reacting with an anhydride. (POH) and (PNH ₂ ) preferably have a hydroxyl group or a primary amino group at one end.

(Polymer having at least one terminal hydroxyl group (POH), polymer having at least one terminal primary amino group (PNH ₂ ))
Preferred examples of the polymer having a hydroxyl group at at least one terminal (POH) or the polymer having a primary amino group at at least one terminal (PNH ₂ ) include those represented by the general formula (II) Is preferred.

(In the general formula (II), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and X ² represents —O—, —S— Or —N (R ^b ) —, wherein R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, G ¹ is a repeating group represented by —R ¹¹ O— G ² represents a repeating unit represented by —C (═O) R ¹² O—, and G ³ represents a unit represented by —C (═O) R ¹³ C (═O) —OR ¹⁴ O—. R ¹¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and R ¹² represents a linear chain having 1 to 8 carbon atoms. or branched alkylene group, or an cycloalkylene group having a carbon number of 4 ~ 8, R ¹³ represents a linear or branched alkylene group having 2 to 6 carbon atoms, a carbon Linear or branched alkenylene group having 2 to 6, an arylene group of a cycloalkylene group, or a C 6-20 carbon atoms 3 ~ 20, R ¹⁴ ^{are, -CH (R 15) -CH (} R ¹⁶⁾ - represents, R ¹ ⁵ and R ¹⁶ are either hydrogen atom while the other alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, 6 to 20 carbon atoms An aryl group, an alkyloxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, an alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, an aryl moiety having 6 to 20 carbon atoms, and the aryl moiety substituted with a halogen atom Represents an optionally substituted aryloxymethylene group or N-methylene-phthalimide group, Z ¹ represents —OH or —NH ₂ , and R ¹⁷ represents a linear or branched group having 2 to 8 carbon atoms. No Killen group, a cycloalkylene group having a carbon number of 3 ~ 8, -C (= O ) R 12 -, or ^{-C (= O) R 13 C} (= O) -OR 14 - is .m1 representing a 0-100 M2 represents an integer of 0 to 60, and m3 represents an integer of 0 to 30. However, m1 + m2 + m3 is 1 or more and 100 or less, and the repeating units G ¹ to G ^{3 in} the general formula (II) The arrangement does not limit the order, and in the polymer represented by the general formula (II), the repeating units G ¹ to G ³ are included in any order between the group X ² and the group R ^17. Further, the repeating units G ¹ to G ³ may be either random type or block type, respectively. )

Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms. From the viewpoints of reducing the viscosity and storage stability of the pigment dispersion, it is preferable that the alkyl group is a branched or branched alkyl group.

In another embodiment, Y ¹ preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the (D-1) dispersant. When m2 = 0 and m3 = 0, Y ¹ is preferably a linear or branched alkyl group having 1 to 7 carbon atoms or has an ethylenically unsaturated double bond.
In order to have an ethylenically unsaturated double bond, it is necessary to have a group having an ethylenically unsaturated double bond. Examples of such a group include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferable. The type of the group having a double bond may be one type or a plurality of types.

X ² represents —O—, —S—, or —N (R ^b ) —, preferably —O— or —N (R ^b ) —.
R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. As the linear or branched alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, cyclohexyl group and the like.

Z ¹ represents —OH or —NH _2, and preferably —OH.

G ¹ represents a repeating unit represented by —R ¹¹ O—, and R ¹¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 3 to 8 carbon atoms. Specific examples of the alkylene group or cycloalkylene group represented by R ¹¹ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopentylene group, and a cyclohexylene group.

G ² represents a repeating unit represented by —C (═O) R ¹² O—, wherein R ¹² is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene having 4 to 8 carbon atoms. Represents a group. Specific examples of the alkylene group or cycloalkylene group represented by R ¹² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopentylene group, and a cyclohexylene group.

G ³ represents a repeating unit represented by —C (═O) R ¹³ C (═O) —OR ¹⁴ O—, wherein R ¹³ is a linear or branched alkylene group having 2 to 6 carbon atoms, carbon It represents a linear or branched alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. Specific examples of the alkylene group or cycloalkylene group represented by R ¹³ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopentylene group, and a cyclohexylene group. Specific examples of the alkenylene group represented by R ¹³ include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, and the like. Specific examples of the arylene group represented by R ¹³ include a phenylene group, a naphthylene group, and an anthracenylene group.
R ¹⁴ represents —CH (R ¹⁵ ) —CH (R ¹⁶ ) —. One of R ¹⁵ and R ¹⁶ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl moiety having 1 carbon atom. An alkyloxymethylene group of -20, an alkenyloxymethylene group having 2-20 carbon atoms in the alkenyl moiety, an aryloxymethylene group in which the aryl moiety has 6-20 carbon atoms, and the aryl moiety may be substituted with a halogen atom, Or represents an N-methylene-phthalimide group.
As the alkyl group having 1 to 20 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 isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group.
The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.
The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, and specific examples include a phenyl group, a naphthyl group, and an anthracenyl group.
The alkyloxymethylene group having 1 to 20 carbon atoms in the alkyl moiety is an embodiment in which an oxymethylene group is bonded to the alkyl group having 1 to 20 carbon atoms represented by R ¹⁴ , and the alkyl group having 1 to 20 carbon atoms is , R ¹⁴ represents the same as the alkyl group having 1 to 20 carbon atoms, and the preferred range is also the same.
The alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety is an embodiment in which an oxymethylene group is bonded to the alkenyl group having 2 to 20 carbon atoms represented by R ¹⁴ , and the alkenyl group having 2 to 20 carbon atoms is , R ¹⁴ represents the same as the alkenyl group having 2 to 20 carbon atoms, and the preferred range is also the same.
The aryloxymethylene group having 6 to 20 carbon atoms in the aryl moiety is an embodiment in which an oxymethylene group is bonded to the aryl group having 6 to 20 carbon atoms represented by R ¹⁴ , and the aryl group having 6 to 20 carbon atoms is , R ¹⁴ represents the same as the aryl group having 6 to 20 carbon atoms, and the preferred range is also the same.

R ¹⁷ represents a linear or branched alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, —C (═O) R ¹² —, or —C (═O) R ¹³ C (= O) —OR ¹⁴ — is represented. Specific examples of the alkylene group or cycloalkylene group represented by R ¹⁷ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclopentylene group, and a cyclohexylene group. R ¹² and R ¹³ have the same meanings as R ¹² and R ¹³ described above, and preferred ranges are also the same.

As a method for synthesizing the compound represented by the general formula (II), it can be synthesized by a known method. For example, the description in paragraphs 0047 to 0082 of JP-A-2007-131832 can be referred to, and the contents thereof are described in the present specification. Embedded in the book.
As the carboxylic acid dispersant used in the present invention, a carboxylic acid dispersant obtained by ring-opening addition with an ε-caprolactone compound and a δ-valerolactone compound is preferably used.

A preferred form of the polymer having at least one terminal hydroxyl group (POH) or the polymer having at least one terminal amino acid group (PNH ₂ ) is, for example, represented by the general formula (III). Those are also preferable.

(In the general formula (III), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and X ² represents —O—, —S— Or —N (R ^b ) —, wherein Rb represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and Z ¹ represents —OH or —NH ₂ .
G ⁴ and G ⁵ each represent a repeating unit represented by C (═O) R ¹² O—, wherein R ¹² is a linear or branched alkylene group having 1 to 8 carbon atoms, or 4 to 8 carbon atoms. Represents a cycloalkylene group. However, R ¹² in R ¹² and G ⁵ in G ⁴ are mutually different groups. R ²⁰ represents —C (═O) R ¹² . m4 represents an integer of 5 to 60, and m5 represents an integer of 5 to 60. The arrangement of the repeating units G ⁴ and G ^{5 in} the general formula (III) is not limited to the order thereof, and in the polymer represented by the general formula (III), between the group X ² and the group Z ¹ Indicates that the repeating units G ⁴ and G ⁵ are included in an arbitrary order, and these repeating units G ⁴ and G ⁵ may be either random type or block type, respectively. )

In the general formula (III), Y ¹ is the formula (II) in the same meaning as Y ^1, and preferred ranges are also the same. When m5 = 0, Y ¹ is preferably a linear or branched alkyl group having 1 to 7 carbon atoms, or has an ethylenically unsaturated double bond.

In the general formula (III), X ² has the general formula (II) in the same meaning as X ^2, and preferred ranges are also the same.
In the general formula (III), Z ¹ has the general formula (II) in the same meaning as Z ¹ in the preferred range is also the same.

G ⁴ and G ⁵ each represent a repeating unit represented by C (═O) R ¹² O—, wherein R ¹² is a linear or branched alkylene group having 1 to 8 carbon atoms, or 4 to 8 carbon atoms. Represents a cycloalkylene group. However, R ¹² in R ¹² and G ⁵ in G ⁴ are mutually different groups. G ⁴ and G ⁵ are synonymous with G ² in the general formula (II), and preferred ranges thereof are also the same. R ¹² in the general formula (III) has the same meaning as the general formula (II) R ¹² in the preferred ranges are also the same.

R ²⁰ represents —C (═O) R ¹² . R ¹² has the same meaning as R ¹² in formula (II), and the preferred range is also the same.

As a method for synthesizing the compound represented by the general formula (III), it can be synthesized by a known method. For example, the description in paragraphs 0046 to 0087 of JP 2010-189514 A can be referred to, and the contents thereof are described in the present specification. Embedded in the book.
As the carboxylic acid dispersant used in the present invention, a carboxylic acid dispersant obtained by ring-opening addition with an ε-caprolactone compound and a δ-valerolactone compound is preferably used.

(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 and the like.

Examples of the aromatic tricarboxylic acid anhydride include benzene tricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid anhydride), etc.), Naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene tricarboxylic acid Acid anhydride, etc.), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2′-biphenyltricarboxylic acid anhydride, 3,4,4′-biphenylmethanetricarboxylic acid anhydride, 3,4,4′-biphenyl Sulfonic tricarboxylic acid anhydrides.

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

Examples of the tetracarboxylic dianhydride 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 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 Bicyclo [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'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic 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 Lacarboxylic acid dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furantetracarboxylic acid 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, 9 , 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, 3,4-dicarboxy-1,2 , 3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

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. Further, 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.

(Reaction of polymer having at least one terminal hydroxyl group (POH) or polymer having at least one terminal primary amino group (PNH ₂ ) with tricarboxylic acid anhydride or tetracarboxylic acid dianhydride)
The carboxylic acid-based dispersant in the present invention is a hydroxyl group of “polymer having a hydroxyl group at at least one terminal (POH)” or the above-mentioned polymer having a primary amino group at at least one terminal (PNH ₂ ). Can be obtained by reacting a tricarboxylic acid anhydride or a tetracarboxylic dianhydride anhydride group.

The number of moles of the hydroxyl group of the polymer (POH) or the primary amino group of the polymer (PNH ₂ ) is <H>, and the number of moles of the carboxylic acid anhydride group of the tricarboxylic anhydride or tetracarboxylic dianhydride is <N. >, The reaction ratio is preferably 0.5 <H> / <N><1.2, more preferably 0.7 <H> / <N><1.1, and most preferably <H This is a case where> / <N> = 1. When the reaction is carried out with <H> / <N><1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.

A catalyst may be used for the reaction of the polymer (POH) or polymer (PNH ₂ ) with the tricarboxylic acid anhydride or tetracarboxylic dianhydride. As the catalyst, for example, a tertiary amine compound can be used. For example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7- Examples include undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene.

The reaction of the polymer (POH) or polymer (PNH ₂ ) with the tricarboxylic acid anhydride or tetracarboxylic dianhydride may be performed 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 reaction temperature of the polymer (POH) or polymer (PNH ₂ ) and the tricarboxylic acid anhydride or tetracarboxylic dianhydride is the case where “polymer having at least one terminal hydroxyl group (POH)” is used. Is preferably performed in the range of 80 ° C. to 180 ° C., more preferably 90 ° C. to 160 ° C. When the reaction temperature is less than 80 ° C., the reaction rate is slow. When the reaction temperature exceeds 180 ° C., the acid anhydride that has reacted and opened a ring may form a cyclic anhydride again, and the reaction may be difficult to complete. In the case of using a “polymer having a primary amino group at at least one end (PNH ₂ )”, it is preferably performed in the range of 0 to 150 ° C., more preferably 10 to 100 ° C. If it is less than 0 ° C., the reaction may not proceed, and if it exceeds 150 ° C., imidation may occur.

-(D-2) Phosphoric acid dispersant represented by the general formula (3)-
The composition of the present invention preferably has (D-2) a phosphoric acid dispersant represented by the general formula (3).

General formula (3)

(In the general formula (3), R ³ represents a polyester structure having a number average molecular weight of 400 to 30000, and y represents 1 or 2. When y is 2, a plurality of R ³ may be the same or different. May be good.)

R ³ represents a polyester structure having a number average molecular weight of 400 to 30,000, and when y is 2, a plurality of R ³ may be the same or different. The number average molecular weight of the polyester structure is more preferably 1900 to 10000, still more preferably 400 to 3000, and particularly preferably 2000 to 3000. If it is less than 400, it cannot be used because it lacks pigment dispersibility.

Examples of the polyester structure include polyester structures having a polyester group obtained by ring-opening polymerization of a lactone monomer, a styrene group, an acryloyl group, a cyanoacryloyl group, a methacryloyl group, a vinyl ether group, and the like. The resulting polyester group is preferred.
When y is 2, R ³ preferably has a polyester structure obtained by ring-opening polymerization of two or more different lactone monomers.

In the phosphate dispersant represented by the general formula (3), R ³ may be a single type of phosphate ester, or a plurality of types of phosphate esters composed of different R ³ may be used. Moreover, the phosphoric acid type | system | group dispersing agent of y = 1 may be individual, and the mixture of the phosphoric acid type dispersing agent of y = 1 and the phosphoric acid type dispersing agent of y = 2 may be sufficient.
When the phosphoric acid ester represented by the general formula (3) has an abundance ratio of the phosphoric acid dispersant with y = 1 and the phosphoric acid dispersant with y = 2 from 100: 0 to 100: 30, the pigment dispersibility Is preferable.

In addition, it is preferable that R ³ of the phosphoric acid dispersant represented by the general formula (3) has a polycaprolactone structure having a number average molecular weight of 400 to 10,000 because the pigment dispersibility is good. More preferably, it is 400 to 3000.

Furthermore, R ³ of the phosphoric acid dispersant represented by the general formula (3) is preferably represented by the following general formula (11).
Formula (11)
R ¹² —O—R ¹³ — (O—R ¹⁴ ) _S
(Wherein R ¹² represents an alkylene group, R ¹³ represents a trihydric or higher polyhydric alcohol structure, R ¹⁴ represents an acryloyl group, a cyanoacryloyl group, or a methacryloyl group, and s represents 2 or more.)

R ¹² is preferably an alkylene group having 8 or less carbon atoms. Further, from the viewpoint of pigment dispersibility, s is preferably 2 or more. In this case, R ¹⁴ may be a different group. s is more preferably 2 to 5, and 2 is particularly preferable.

Examples of the trihydric or higher polyhydric alcohol used in R ¹³ include glycerin, propyl alcohol, pentaerythritol, and dipentaerythritol. Particularly preferred are trivalent to hexavalent ones.

The acid value of the phosphoric acid dispersant is preferably 10 to 500 mgKOH / g, more preferably 30 to 350 mgKOH / g, and further preferably 120 to 200 mgKOH / g.

The phosphoric acid dispersant can be produced by a known method. For example, the description in paragraphs 0037 to 0051 of JP-A-2007-231107 can be referred to, and the contents thereof are incorporated herein.
As the phosphoric acid dispersant used in the present invention, a phosphoric acid dispersant obtained by ring-opening addition of ε-caprolactone and δ-valerolactone is preferably used.

-(D-3) a copolymer containing a structural unit represented by either general formula (1) or general formula (2)-The composition of the present invention comprises (D-3) the following general formula (1) And a copolymer containing a structural unit represented by any of the following general formula (2).

In the above general formulas (1) and (2), R ¹ to R ⁶ each represents a hydrogen atom or a monovalent organic group, and X ¹ and X ² represent —CO—, —C (= O) represents O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each represent a single bond or a divalent organic linking group, and A ¹ and A ² Each represents a monovalent organic group, m and n each represents an integer of 2 to 8, and p and q each represents an integer of 1 to 100.

In general formulas (1) and (2), R ¹ to R ⁶ each represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, and a cyclohexyloxy group. Etc.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, Examples thereof include a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.
In general formulas (1) and (2), R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are each a hydrogen atom or a methyl group on the pigment surface. It is most preferable from the viewpoint of adsorption efficiency.

In the general formulas (1) and (2), X ¹ and X ² each represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. . Among them, —C (═O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of adsorptivity to the pigment, and —C (═O) O— is most preferable.

In general formulas (1) and (2), L ¹ and L ² each represent a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Among these, an oxygen atom and a nitrogen atom are preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The divalent organic linking group includes a hetero atom or a hetero atom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the end of the above alkylene group. A compound having a partial structure and linked to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom is preferable from the viewpoint of adsorptivity to the pigment. Here, the adjacent oxygen atom means an oxygen atom that binds to L ¹ in the general formula (1) and L ² in the general formula (2) on the side chain end side.

In general formulas (1) and (2), A ¹ and A ² each represent a monovalent organic group. As the monovalent organic group, a hydroxyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is preferable.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), Zia Kiruhosuhono group _{_{(-PO 3 (alkyl) 2)}} , diaryl phosphono group _{_{(-PO 3 (aryl) 2)}} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (- PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group) ), Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO _3). (aryl) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono Alkoxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

Examples of the substituent include alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl , Can be exemplified phosphonophenyl phenyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a carbon number having 5 to 20 carbon atoms. Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. Even more preferred are linear alkyl groups of 6 to 10 and branched alkyl groups of 6 to 12 carbon atoms.

In general formulas (1) and (2), m and n each represent an integer of 2 to 8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

In general formulas (1) and (2), p and q each represent an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

The copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) includes the repeating unit represented by the general formula (1) from the viewpoint of dispersion stability. Those are preferred.

The repeating unit represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (1) -2.

General formula (1) -2

In the general formula (1) -2, R ¹ to R ³ each represents a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents —C (═O) — or —NHC (═O) —, A ¹ represents a monovalent organic group, m represents an integer of 2 to 8, and p represents an integer of 1 to 100 .

The repeating unit represented by the general formula (1), (2), or (1) -2 is a simple unit represented by the following general formula (i), (ii), or (i) -2, respectively. The polymer is introduced as a repeating unit of the polymer compound by polymerization or copolymerization.

In the general formulas (i), (ii), and (i) -2, R ¹ to R ⁶ each represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² are each — CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each represents a single bond or a divalent organic linking group. La represents an alkylene group having 2 to 10 carbon atoms, Lb represents —C (═O) — or —NHC (═O) —, and A ¹ and A ² each represents a monovalent group. Represents an organic group, m and n each represents an integer of 2 to 8, and p and q each represents an integer of 1 to 100.

In the following, preferred specific examples of the monomer represented by the general formula (i), (ii), or (i) -2 are those described in paragraphs 0081 to 0084 of JP2012-173356A. Examples of the monomers (XA-1) to (XA-23) are shown, but the present invention is not limited thereto.

The copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) is selected from the repeating units represented by any one of the general formulas (1) and (2). It is sufficient that at least one type of repeating unit is included, and only one type may be included, or two or more types may be included.

Moreover, in the copolymer containing the structural unit represented by either the general formula (1) or the following general formula (2), the inclusion of the repeating unit represented by any of the general formulas (1) and (2) The amount is not particularly limited, but when the total repeating unit contained in the polymer is 100% by mass, the repeating unit represented by any one of the general formulas (1) and (2) is 5% by mass or more. The content is preferably 50% by mass, more preferably 50% by mass to 80% by mass.

The copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) is a monomer having a functional group capable of adsorbing to the pigment for the purpose of enhancing adsorption to the pigment. And a polymer compound obtained by copolymerizing the above-described monomers represented by the general formulas (i), (ii), and (i) -2.
Specific examples of the monomer having a functional group capable of adsorbing to the pigment include a monomer having an acidic group, a monomer having an organic dye structure or a heterocyclic structure, a monomer having a basic nitrogen atom, and an ionic group. A monomer etc. can be mentioned. Of these, monomers having an acidic group, and monomers having an organic dye structure or a heterocyclic structure are preferable from the viewpoint of adsorption to the pigment.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono (meth) acrylate and the like can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride from the viewpoint of developing removability of unexposed areas. An addition reaction product with a cyclic anhydride such as

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

The copolymer containing a structural unit represented by any one of the general formula (1) and the following general formula (2) preferably contains a repeating unit derived from a monomer having an acidic group as described above. By including such a repeating unit, when the composition of the present invention is applied to a colored photosensitive resin composition, the development removability of an unexposed portion is excellent.

The copolymer containing the structural unit represented by any of the general formula (1) and the following general formula (2) may contain only one type of repeating unit derived from a monomer having an acidic group. And two or more types may be included.
In the copolymer including the structural unit represented by any one of the general formula (1) and the following general formula (2), the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. And particularly preferably 50 mg KOH / g to 200 mg KOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, repeating units derived from monomers having acidic groups The content of is preferably 50 mgKOH / g to 200 mgKOH / g.

Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, specific monomers, maleimides, and maleimide derivatives described in JP-A-2009-256572, paragraph numbers 0048 to 0070. 1 type selected from a group is mentioned.

Examples of the monomer having a basic nitrogen atom include (meth) acrylic acid ester, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and (meth) acrylic acid. 1- (N, N-dimethylamino) -1,1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N (meth) acrylic acid, N-diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth ) Piperidinoethyl acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyro (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N, N-methylaminoethyl). N'-dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylamino) Propyl) acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2 -(N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) Acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl Examples include (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, and styrenes. N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene and the like.

It is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include the monomers described in paragraph No. 0095 of JP2012-173356A, the contents of which are incorporated herein.

Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers). Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having the acidic group and salts of organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol). As the monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride or benzyl bromide; methanesulfonic acid Alkyl sulfonic acid ester (alkyl group: C1-18); aryl sulfonic acid alkyl ester such as benzenesulfonic acid, toluenesulfonic acid (alkyl group: C1-18); dialkyl sulfate (alkyl group: C1-4), etc. Quaternized, dialkyl diallyl ammo The presence or absence salts.

The monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of the pigment to be dispersed, and these may be used alone or in combination of two or more.

The copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) further includes a repeating unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired. May be included.

Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, phenyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 2-methoxy (meth) acrylate Chill, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, (meth ) Acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (Meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonylphenoxypolyethylene glycol, (meth) acrylic acid di Cyclopentenyl, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopenta (meth) acrylate Nyl, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

A preferred embodiment of the copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) is represented by at least the general formula (i), (ii), or (i) -2. And a monomer having an acidic group, or a monomer having an organic dye structure or a heterocyclic structure, and more preferably represented by at least the general formula (i) -2. And a monomer having an acid group are copolymerized.
According to this embodiment, it is possible to provide a composition that is excellent in pigment adsorption and excellent in developability.

In the present invention, the following (D-3) dispersants are particularly preferable.

-(D-4) Graft copolymer containing nitrogen atom in main chain-
The composition of the present invention preferably has (D-4) a graft copolymer containing a nitrogen atom in the main chain. The graft copolymer containing a nitrogen atom in the main chain preferably has a repeating unit represented by the formula (A) and / or a repeating unit represented by the formula (B).

(In the formula (A), R ₁ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any of the following formulas (C) to (E).)

In the above formula (A), R ¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably ethylene. It is a group. A represents a hydrogen atom or any one of the following formulas (C) to (E), preferably formula (C).

In said formula (B), R < ¹ > and A are synonymous with R < ¹ > and A in formula (A).

In the above formula (C), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, hexylene and the like is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (D), Y ¹ represents a divalent linking group. Among them, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy are included. preferable. W ² represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene and butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene and propylene is preferable. Y ² represents a hydrogen atom or —CO—R ² (R ² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc .; To 5 alkyl groups are preferred). q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (E), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups. Among them, an alkyl group having 10 to 20 carbon atoms such as stearyl, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferred.
The content of the repeating unit represented by the formula (A) or (B) in the “graft copolymer containing nitrogen atom” is preferably higher, and is usually 50 mol% or more, preferably 70 mol%. That's it. The repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) may be both present, and the content ratio is not particularly limited, but the repeating unit represented by the formula (A) It is preferable to contain a large amount of. The total number of repeating units represented by the formula (A) or the formula (B) is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50. Moreover, repeating units other than Formula (A) and Formula (B) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The “graft copolymer containing a nitrogen atom” preferably has —NH ₂ and —R ¹ —NH ₂ (R ¹ is as defined above for R ¹ ) at the ends.

The “graft copolymer containing nitrogen atom” may have a main chain which is linear or branched. The amine value of the graft copolymer is usually 5 mgKOH / g to 100 mgKOH / g, preferably 10 mgKOH / g to 70 mgKOH / g, more preferably 15 mgKOH / g to 40 mgKOH / g or less.
When the amine value is 5 mgKOH / g or more, the dispersion stability can be further improved, and the viscosity can be further stabilized. When the amine value is 100 mgKOH / g or less, the residue can be further suppressed, and a decrease in electrical characteristics after the liquid crystal panel is formed can be further suppressed.

The weight average molecular weight of the above “graft copolymer containing nitrogen atom” measured by GPC is preferably from 3000 to 100,000, particularly preferably from 5,000 to 50,000. When the weight average molecular weight is 3000 or more, aggregation of the coloring material can be further suppressed, and higher viscosity and gelation can be further suppressed. When it is 100,000 or less, the viscosity increase of the copolymer itself can be further suppressed, and the lack of solubility in the organic solvent can be further suppressed.

In the present invention, the following (D-4) dispersants are particularly preferable.

As the method for synthesizing the above (D-4) dispersant, a known method can be adopted, for example, a method described in JP-B-63-30057 can be used.

The molecular weight of the dispersant used in the present invention is preferably 2,000 to 50,000, more preferably 5,000 to 30,000 in terms of weight average molecular weight (Mw).
The content of the (C) pigment dispersant is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the total pigment.
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.
Moreover, about (A) pigment and (B) pigment, respectively, the same dispersing agent may be used and a different dispersing agent may be used. The (A) pigment and the (B) pigment may be separately dispersed or co-dispersed. Preferably, the (A) pigment and the (B) pigment are separately dispersed.

<< (E) Pigment derivative >>
The composition of the present invention has (E) a pigment derivative. (E) The pigment derivative is preferably a compound having a structure in which a part of the pigment is substituted with a basic group. (E) As pigments for constituting the pigment derivative, quinoline pigments, benzimidazolone pigments, isoindoline pigments, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments Examples include pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.
(E) The pigment derivative is preferably a quinoline-based, benzimidazolone-based, or isoindoline-based pigment derivative, and more preferably a benzimidazolone-based pigment derivative.

As a basic group which a pigment derivative has, an amino group is preferable. Examples of such a compound include the following compounds.

Examples of the pigment derivative (E) used in the present invention include a pigment derivative represented by the following general formula (I), a pigment derivative represented by the general formula (II), and a pigment derivative represented by the general formula (III). It is preferable that there is at least one. Hereinafter, the pigment derivative represented by the following general formula (I), the pigment derivative represented by the general formula (II), and the pigment derivative represented by the general formula (III) will be described.

-Pigment derivatives represented by the general formula (I)-

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 through 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, monoazo dyes having a benzimidazolone skeleton are 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. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more 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 arylene group 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 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 the alkyl group, 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 isobutyl 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 an integer of 1 to 6, preferably 1 to 4, and more preferably 1 to 3.
n represents an integer of 1 to 4, preferably 1 to 3, and more preferably 1 or 2.

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

Formula (I-1)

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 in general formula (I-1) each represents an alkyl group which may have a substituent, and have the same meaning as R ¹ and R ² in general formula (I), and the preferred ranges are also the same It is. In the general formula (I-1), R ¹ and R ² preferably represent an alkyl group which may have the same substituent. Further, R ¹ and R ² in the general formula (I-1) is preferably also have the same substituents as R ¹ and R ² in the general formula (I) represents an alkyl group.

M represents an integer of 1 to 6, preferably 1 to 4, and more preferably 1 to 3. m preferably represents the same integer as m in formula (I).

Hereinafter, specific examples of the pigment derivative used in the present invention will be shown, but the present invention is not limited thereto.

-Pigment derivatives represented by general formula (II)-
Formula (II)

(In General Formula (II-1), Y ¹ represents —NR′— or —O—, and Y ² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenylene group having 2 to 20 carbon atoms which may be substituted, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O— , —SO ₂ —, and —CO— may be bonded to each other through a divalent linking group, R ′ is a hydrogen atom, and may have a substituent and has 1 to 20 carbon atoms. R ¹ and R ² represent an alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. Each of the alkyl groups having 1 to 20 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent. .R ¹ and R ² representing the 0 alkenyl groups together, further nitrogen atom, heterocyclic structure which may be substituted include an oxygen atom or a sulfur atom may be formed.
In general formula (II-2), Z ¹ is a single bond connecting the triazine ring and the 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 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 substituent Represents an arylene group having 6 to 20 carbon atoms which may have a group, and R ′ and R ″ each represents a hydrogen atom and 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. 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. an alkenyl group having 1-20 or carbon atoms, which may have a substituent or an aryl group of 6 to 20, alkyl group of R ⁷ is - 1 carbon atoms, which may have a substituent group 20, Alternatively, it represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent. )

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-3).
Formula (II-3)

(In General Formula (II-3), D and E are each formed 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 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, an aromatic or heterocyclic group which may have a substituent, hydroxyl group Groups, alkoxy groups having 1 to 3 carbon atoms (for example, methoxy group, ethoxy group, propoxy group), carboxyl groups or salts thereof, esters having 1 to 20 carbon atoms, amides having 1 to 20 carbon atoms, sulfone groups or salts thereof , A sulfamoyl group, —NR′R ″ —, and 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 substituted group. An aryl group having 6 to 20 carbon atoms which may have a group.
As the alkyl group having 1 to 20 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 isobutyl 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, preferably an integer of 0 to 3, more preferably 2 to 3, and still more preferably 4.

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 preferred. 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, Alternatively, it represents an aryl group having 6 to 20 carbon atoms which may have a substituent, and a hydrogen atom is preferable.
The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group.
The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.
The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, and specific examples include a phenyl group, a naphthyl group, and an anthracenyl group.
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. 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 thereof 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 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 groups represented by the following general formula (II-1) or (II-2), —O— (CH ₂ ) _n —R ⁸ , —OR ⁹ , —NR ¹⁰ R, respectively. ¹¹ represents a group selected from —Cl, —F or —X ³ —X ² —X ¹ —Dye, and one of A and B is represented by the following general formula (II-1) or (II-2): Or a group represented by —O— (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 (II-1) or the following general formula (II-2), and A and B are represented by the following general formula (II-1) or the following general formula ( More preferably, it is a group represented by II-2), and 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 alkyl group having 2 to 20 carbon atoms which may have a substituent. It represents an alkenyl group or an aryl group having 6 to 20 carbon atoms which may have 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.

Formula (II-1)

(In General Formula (II-1), Y ¹ represents —NR′— or —O—, and Y ² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenylene group having 2 to 20 carbon atoms which may be substituted, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, —O— , —SO ₂ —, and —CO— may be bonded to each other through a divalent linking group, R ′ is a hydrogen atom, and may have a substituent and has 1 to 20 carbon atoms. R ¹ and R ² each represents an alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. In each case, the alkyl group having 1 to 20 carbon atoms which may have a substituent, or 2 to 20 carbon atoms which may have a substituent. An alkenyl 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 an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted alkenylene group having 2 to 20 carbon atoms, or an optionally substituted group. And an arylene group having 6 to 20 carbon atoms, and these groups are bonded to each other through 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 ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene 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 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.
The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group.
The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples include an ethenyl 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.

Formula (II-2)

(In the general formula (II-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′—, wherein 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 Represents an arylene group having 6 to 20 carbon atoms which may have a substituent, and R ′ and R ″ each represent a hydrogen atom and an alkyl having 1 to 20 carbon atoms which may have a substituent. R ³ represents an optionally substituted alkenyl group having 2 to 20 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms 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 to 20 carbon atoms that may have a substituent. 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 a substituted group. Represents an alkenyl group having 2 to 20 carbon atoms which may have a group.)

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, Alternatively, it represents an aryl group having 6 to 20 carbon atoms which may have a substituent. R ′ and R ″ have the same meaning as R ′ in formula (II-1), and the preferred range is also the same.
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 an optionally substituted carbon. It represents an arylene group having a number of 6 to 20. G has the same meaning as Y ² in formula (II-1), and the preferred range is 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 meanings as R ′ in formula (II-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 (II-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, specific examples of the pigment derivative represented by the general formula (II) used in the present invention are shown, but the present invention is not limited thereto.

-Pigment derivatives represented by the general formula (III)-

In general formula (III), A represents a component capable of forming an azo pigment together with XY. A can be arbitrarily selected as long as it is a compound capable of forming an azo pigment by coupling with a diazonium compound. Specific examples of A will be shown below, but the present invention is not limited to these specific examples.

In the general formula (III), X represents a single bond (meaning that Y is directly connected to —N═N—) or a group selected from divalent linking groups in the following group A. To express.

In the general formula (III), Y represents a group represented by the following general formula (III-2).

In the general formula (III-2), Z represents an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. R ² represents an alkyl group having 1 to 4 carbon atoms or a 5- or 6-membered saturated heterocyclic ring containing a nitrogen atom. When R ² represents a 5- or 6-membered saturated heterocyclic ring containing a nitrogen atom, a heterocyclic ring represented by the following structural formula is preferable.

In the general formula (III-2), Z and —NR ² may each have a lower alkyl group or an alkoxy group as a substituent. In the general formula (III-2), a represents 1 or 2, preferably 2.

Specific examples (specific examples 1 to 22) of the compound represented by the general formula (III) are shown below, but the present invention is not limited to these specific examples.

As content of (E) pigment derivative in this invention, it is preferable that they are 0.5 mass part or more and 50 mass parts or less with respect to 100 mass parts of all the pigments, and it is 1 mass part or more and 25 mass parts or less. Is more preferable.
Only one pigment derivative may be contained in the composition of the present invention, or two or more pigment derivatives may be contained therein. When two or more types are included, the total amount is preferably within the above range.
Moreover, about the (A) pigment and the (B) pigment, the same pigment derivative may be used, respectively, and a different pigment derivative may be used. Moreover, a pigment derivative may be used for both the (A) pigment and the (B) pigment, or only one of them may be used. In the composition of this invention, it is preferable that 80 mass% or more of the pigment derivative used for (A) pigment and (B) pigment is common. By setting it as such a structure, the increase in the viscosity of a composition is suppressed and compatibility becomes good and the effect of invention is exhibited more effectively.

<< other ingredients >>
In addition to the components described above, the composition of the present invention is further in the range that does not impair the effects of the present invention, and further (F) a photopolymerization initiator, (G) a polymerizable compound, and (H) polymerizable to a side chain. Other components such as a resin having a double bond, an organic solvent, and a crosslinking agent may be included.

<< (F) Photopolymerization initiator >>
The composition of this invention may contain 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 to 800 nm (more preferably 330 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 (oxime polymerization initiators) 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 triarylimidazole 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 forming a fine pattern in a solid-state imaging device, a stepper exposure machine is used for exposure for curing. However, this exposure machine may be damaged by halogen, and the addition amount of the polymerization initiator needs to be kept low. Therefore, in view of these points, it is most preferable to use an oxime compound as the photopolymerization initiator (F) in order 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), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound 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-tribromomethyl-5-styryl-1,3,4 -Oxadiazole and the like).

Further, as photopolymerization initiators other than those mentioned above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, etc. Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (eg, 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'-ca Bonylbis (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 No. 2002-363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphos Zinc oxide, 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.) Examples thereof include compounds described in JP-A Nos. 53-133428, 57-1819, 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) benzophenones (eg, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4'-dimethylamino Benzophenone, 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, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferable examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

Examples of oxime compounds such as oxime derivatives that are preferably used as the photopolymerization initiator 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 Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No. 7,556,910 contained therein, 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 cyclic oxime compounds, in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
Further, the compounds described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because high sensitivity can be achieved by regenerating the active radical from the polymerization inert radical. it can.

Most preferably, an oxime compound having a specific substituent as disclosed in JP 2007-26997A and an oxime compound having a thioaryl group as disclosed in JP 2009-191061 A can be given.
Specifically, the oxime compound that is a photopolymerization initiator is preferably a compound represented by the following general formula (OX-1). The oxime N—O bond 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 represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent 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.

As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group , Isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, phenacyl, 1-naphthoylmethyl, 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-nitro Enashiru 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, m-cumenyl and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, turnanaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylyl Nyl group, phenalenyl group, fluorenyl group, anthryl group, biantra Nyl 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.

The acyl group is preferably an acyl group having 2 to 20 carbon atoms, and specifically includes 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, and specifically includes 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-fluoropheny Oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and, 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 include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and 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 a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, a 4-phenylsulfanylphenylthiocarbonyl group, and a 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 the 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 (eg vinyl group, allyl group) alkylene group, aryl group (eg 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 in terms 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 represent a monovalent substituent, A and Y each represent a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5 is there. 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, X in the general formula (OX-2) is preferably an alkyl group from the viewpoint of solvent solubility and improvement of absorption efficiency in the long wavelength region.
In the formula (2), n represents an integer of 0 to 5, and an integer of 0 to 2 is preferable.

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

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

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 represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents 0 to 5 Is an integer. )
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 a 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 (Vary Inc., Carry-5 spectrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

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

When the composition of this invention contains (F) photoinitiator, content of (F) photoinitiator is 0.1 mass% or more and 10 mass% or less with respect to the total solid of a composition. More preferably, it is 0.5 mass% or more and 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.

<< (G) polymerizable compound >>
The composition of the present invention may contain 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 (a polymerizable compound having 4 or more polymerizable groups) is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.

Such compound groups are 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, compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be preferably 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 Polyfunctional alcohols such as nurate, glycerin and trimethylolethane added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, JP 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.
As other preferable polymerizable compounds, there are fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc., and ethylenically unsaturated groups. A compound having two or more functions, a cardo resin can also be used.

As compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, paragraphs [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 above general formula, n is 0 to 14, and m is 1 to 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 compounds described in paragraphs 0248 to 0251 of JP-A-2007-2699779. It can be suitably used in the invention.

Further, compounds obtained by adding (meth) acrylate after 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 are also provided. It can be used as a polymerizable compound.

Among them, 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. Company-made) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., 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.

The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or 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 preferable, 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 to 40 mgKOH / g, and particularly preferably 5 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. Therefore, 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 value of the entire polyfunctional monomer should be adjusted to be 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 alcohols such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following general formula (Z-1) is preferable.

In the general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six R 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 an integer 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 the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, a 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 (formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ is 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.

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

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
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), — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) — represents an 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.

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) 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), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) 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, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

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 described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described 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 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd., DPHA-40H (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.), etc. It is done.

Examples of the cyclic ether (epoxy, oxetane) include those having an epoxy group such as bisphenol A type epoxy resin, JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003. , JER-1055, JER-1007, JER-1009, JER-1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (manufactured by DIC Corporation), etc., and bisphenol F As type epoxy resins, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON83 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-770, EPICLON® N-775 (above, manufactured by DIC Corp.), etc. As resins, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON 、 N-673, EPICLON N-680, EPICLON N-690 (above, manufactured by DIC Corporation), EOCN-1020 (Below (Manufactured by Nippon Kayaku Co., Ltd.), as aliphatic epoxy resins, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) 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, Daicel) Chemical Industry Co., Ltd.), Denacol® EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corp.), ADEKA® RESIN® EP-4000S, EP-4003S, EP-4010S, EP 4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER-1031S (Japan Epoxy) Resin Co., Ltd.). 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, selection and use of a polymerizable compound is also required for compatibility and dispersibility with other components (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, etc.) contained in the composition of the present invention. The method is an important factor. For example, the 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.

When the composition of the present invention has (G) a polymerizable compound, the content of the polymerizable compound is preferably 5 to 40% by mass, more preferably 5 to 30% by mass with respect to the total solid content in the composition. 5 to 20% by mass is particularly preferable.

<< (H) Resin having a polymerizable double bond in the side chain >>
In the present invention, if necessary, a resin having a polymerizable double bond in the side chain may be contained. 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.

(H) 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.

(H) The polymerizable monomer having 2 to 6 hydroxyl groups constituting the resin having a polymerizable double bond in the side chain (p) 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)

(Wherein R ¹ and R ⁴ each represent a hydrogen atom or 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) Represents an alkylene group of 1 to 4 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, tetrahydrofurfuryl (meth) acrylate, etc. N-vinylpyrrolidone; styrene and its derivatives, styrenes such as α-methylstyrene; acrylamides such as (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide, diacetone (meth) acrylamide; Examples include (meth) acrylonitrile, other vinyl compounds such as 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.

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.

(H) 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 the ethylenically unsaturated double bond introduced into the copolymer (a) via a hydroxyl group is indicated by the “ethylenically unsaturated double bond equivalent” of the resulting resin. The ethylenically unsaturated double bond equivalent of the resin obtained here 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 (H) 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) and the compound (b) having a functional group capable of reacting with a hydroxyl group and 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 (H) a resin having a polymerizable double bond in the side chain, (H) the content of the resin having a polymerizable double bond in the side chain is 100 parts by mass of the resin component. On the other hand, the content is preferably 30 to 100% by mass, more preferably 40 to 90% by mass, and further preferably 50 to 80% by mass.
(H) One type of resin having a polymerizable double bond in the side chain may be contained in the composition of the present invention, or two or more types may be contained. 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, but in particular, the solubility and coating of ultraviolet absorbers, alkali-soluble resins and dispersants, etc. 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 oxyacetates (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 Oxypropionic 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 (for example, 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 Tolue And xylene are preferable.

These organic solvents are preferably mixed in two or more types 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 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 50% by mass is particularly preferred.

-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 kind of substituent In addition, a phenol compound, a naphthol compound, or a hydroxyanthracene compound can be used. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, the description in paragraphs 0134 to 0147 of JP-A No. 2004-295116 can be referred to.
When the composition of the present invention contains a crosslinking agent, 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 to about 5% by mass with respect to the mass of the whole 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 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 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, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 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.) and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of anionic surfactants 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, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
When a surfactant is contained in the composition of the present invention, the addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 2.0% by mass with respect to the total mass of the composition. 1.0% by mass.
The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

-Other additives-
Various additives, for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, 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. Of these, those having a molecular weight of 600 or less, particularly those having 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. Of these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.

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% by weight 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.

In the present invention, it is preferable to mix the pigment with other components after dispersing the pigment with the dispersant. The pigment can be dispersed by mixing (A) a dispersion in which the pigment is dispersed with a dispersant and (B) a dispersion in which the pigment is dispersed with the dispersant.
The composition prepared as described above is preferably filtered after using a filter having a pore size of about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm, and then used. be able to.

Since the composition of the present invention can form a cured film having excellent heat resistance and color characteristics, it is suitably used for forming a color pattern (colored layer) of a color filter. 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 photosensitive resin composition layer forming step of forming (applying) the colored photosensitive resin composition of the present invention on a support to form a colored photosensitive resin composition layer, It includes an exposure step of exposing the colored photosensitive resin composition layer in a pattern-like manner, 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 material such as a substrate.

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

The manufacturing method of the color filter of this invention applies the pattern formation method of this invention, and includes the process of forming a colored pattern on a support body using the pattern formation method of this invention.
That is, the method for producing a color filter of the present invention applies the pattern forming method of the present invention. The colored photosensitive resin composition layer of the present invention is applied to a support to form a colored photosensitive resin composition layer. A colored photosensitive resin composition layer forming step to be formed; an exposure step of exposing the colored photosensitive resin composition layer in a pattern-like manner; and a pattern forming step of developing and removing unexposed portions to form a colored pattern. It is characterized by including. Further, if necessary, a step of baking the colored photosensitive resin composition layer (pre-baking step) and a step of baking the developed colored pattern (post-baking step) may be provided. Hereinafter, these steps may be 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 the present invention applies the pattern forming method of the present invention, and includes forming a colored pattern on the substrate using the pattern forming method of the present 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 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, screen printing method and the like can be applied.

The colored photosensitive resin composition layer coated 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 30 ~ 1500mJ / cm ² is preferably 50 ~ 1000mJ / cm ^2, and most preferably 80 ~ 500mJ / cm ^2.

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and further preferably 0.2 to 0.8 μm.
It is preferable to set the film thickness to 1.0 μm or less because high resolution and high adhesion can be obtained.
In addition, in this step, a cured film having a thin film thickness of 0.7 μm or less can also be suitably formed, and the obtained cured film is developed in a pattern forming process described later, thereby forming a thin film. 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 to 30 ° C., and the development time is conventionally 20 to 90 seconds. In order to remove the residue more, it may be carried out for 120 to 180 seconds in recent years. 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. 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 to 10% by mass, preferably An alkaline aqueous solution diluted with pure water so as to be 0.01 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.
The post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 to 240 ° C., preferably 200 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 coating 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 from 0.1 to 3 μm, more preferably from 0.2 to 2.5 μm, still more preferably from 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, 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 a 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.

Further, the 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 preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

Next, the resist pattern (that is, etching mask) remaining after 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.

Further, examples of the step of removing the resist pattern using the cleaning water include a step 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. Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine. Preferred are monoethanolamine, diethanolamine and triethanolamine, and more preferred is monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of cyclic nitrogen-containing compounds 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, and 2,6-lutidine. 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 includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes 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 a process 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 photosensitive resin composition or pigment in the coating machine occurs. There is a case. 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. Also, 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, etc. 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, 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 described above 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 performed, and the formed colored pattern (colored pixel) has excellent pattern shape, pattern surface roughness and development. 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 Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 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-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".

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

When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue 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 (C) Resin 1 (Synthesis Example 1)>
570 parts of cyclohexanone was placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the reaction vessel. At the same temperature, 23.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 35.0 parts of benzyl methacrylate, As the monomer (a), 22.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.), 48.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyronitrile 3 0.0 part of the mixture was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added to the reaction vessel, and further reacted at 80 ° C. for 1 hour. Subsequently, a transparent resin copolymer solution was obtained. Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 336 parts of the obtained transparent resin copolymer solution at 70 ° C. for 3 hours. The solution was added dropwise to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. With reference to this, the non-volatile content was added to the previously synthesized photosensitive transparent resin solution. A solution of a photosensitive resin was prepared by adding cyclohexanone so that the amount of the resin was 20% by weight. The obtained photosensitive transparent resin 1 (resin 1) had a weight average molecular weight Mw of 21000 and an ethylenically unsaturated double bond equivalent of 470. The acid value was 50 mgKOH / g.

<Synthesis of (C) Resins 2 and 3>
Resins 2 and 3 (C) were obtained in the same manner as in Synthesis Example 1 except that the type and amount of reagent used were changed. Resin 2 has a weight average molecular weight of 11,000, an acid value of 150 mgKOH / g, and does not contain an ethylenically unsaturated double bond. Resin 3 had a weight average molecular weight of 12,000, an acid value of 37 mgKOH / g, and an ethylenically unsaturated double bond equivalent of 963.

<Synthesis of (C) Resins 4-7>
(C) Resins 4 to 7 were obtained by changing the reaction time in the synthesis of resin 1. The weight average molecular weight of Resin 4 was 8000, the acid value was 50 mgKOH / g, and the ethylenically unsaturated double bond equivalent was 470. The weight average molecular weight of the resin 5 was 38000, the acid value was 50 mgKOH / g, and the ethylenically unsaturated double bond equivalent was 470. The weight average molecular weight of the resin 6 was 40000, the acid value was 150 mgKOH / g, and the ethylenically unsaturated double bond equivalent was 470. The weight average molecular weight of the resin 7 was 100,000, the acid value was 50 mgKOH / g, and the ethylenically unsaturated double bond equivalent was 470.

<Synthesis of (C) Resins 8 and 9>
A comparative resin was synthesized with reference to the description in paragraph No. 0043 of Japanese Patent No. 5210286. Specifically, Resin 8 and Resin 9 were obtained with 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, and 15.0 parts of 2-hydroxyethyl methacrylate. The weight average molecular weights of Resins 8 and 9 were 40,000 and 100,000, respectively.

<Synthesis of (C) Resins 10 to 11>
(C) Resins 10 and 11 were obtained by changing the reaction time in the synthesis of resin 2. The resin 10 has a weight average molecular weight of 42,000, an acid value of 150 mgKOH / g, and does not contain an ethylenically unsaturated double bond. Resin 11 has a weight average molecular weight of 75,000, an acid value of 150 mgKOH / g, and does not contain an ethylenically unsaturated double bond.

<(C) Synthesis of Resins 12-13>
(C) Resins 12 and 13 were obtained by changing the reaction time in the synthesis of resin 3. The weight average molecular weight of the resin 12 was 45000, the acid value was 37 mgKOH / g, and the ethylenically unsaturated double bond equivalent was 963. The weight average molecular weight of the resin 13 was 62000, the acid value was 37 mgKOH / g, and the ethylenically unsaturated double bond equivalent was 963.

<Synthesis of (D) Pigment Dispersant 1>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. Then, the mixture was heated and stirred at 120 ° C. for 4 hours. Subsequently, after confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added here, and it was made to react at 120 degreeC for 2 hours. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated to obtain Pigment Dispersant 1. The acid value of the obtained pigment dispersant 1 was 49 mgKOH / g.

<Synthesis of (D) Pigment Dispersant 2>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 186 g of lauryl alcohol, 571 g of ε-caprolactone monomer and 0.6 g of tetrabutyl titanate, and replaced with nitrogen gas, and then heated at 120 ° C. for 3 hours. Stir. The disappearance of the caprolactone monomer was confirmed by a GPC (gel permeation chromatography) RI detector using tetrahydrofuran as an eluent. After cooling this reaction container to 40 degrees C or less, it mixed with 84.5 g of polyphosphoric acid of 116% orthophosphoric acid content, heated up gradually, and heated at 80 degreeC for 6 hours, stirring. This obtained the pigment dispersant 2 which is a phosphoric acid type dispersant represented by the said General formula (3). In the general formula (3), the number average molecular weight of R ³ was 760, and the abundance ratio of y = 1 and 2 was 100: 12. The acid value of the obtained pigment dispersant 2 was 166.

<Preparation of red pigment dispersion>
7.75 parts by weight of a red pigment (CI Pigment Red254), 2.33 parts by weight of a yellow pigment (CI Pigment Yellow 139), 1.12 parts of a pigment derivative shown in Table 1 below, A mixed liquid containing 7.34 parts by mass of the pigment dispersant shown in 1 and 81.46 parts by mass of PGMEA was mixed and dispersed by a bead mill (zirconia beads 0.3 mm diameter) for 3 hours to obtain a pigment. A dispersion was prepared. Thereafter, the pigment dispersion is further subjected to a dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.). I did it. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

<Preparation of red pigment dispersion containing orange pigment>
1.38 parts by weight of red pigment (CI Pigment Red254), 3.02 parts by weight of red pigment (CI Pigment Red177), 1.23 parts by weight of yellow pigment (CI Pigment Yellow 139) , 5.44 parts by mass of an orange pigment (CI Pigment Orange 71), 1.23 parts of the pigment derivative shown in Table 1 below, 6.80 parts by mass of the pigment dispersant shown in Table 1 below, and PGMEA A mixed liquid composed of 80.90 parts by mass was mixed and dispersed by a bead mill (zirconia beads 0.3 mm diameter) for 3 hours to prepare a pigment dispersion. This pigment dispersion was then further subjected to a dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion containing an orange pigment.

<Preparation of green pigment dispersion>
8.96 parts by mass of a green pigment (CI Pigment Green 36 or CI Pigment Green 7), 1.00 parts of the pigment derivative shown in Table 1 below, and 5. 5 of the pigment dispersant shown in Table 1 below. A mixed liquid containing 95 parts by mass and 84.10 parts by mass of PGMEA was mixed and dispersed by a bead mill (zirconia beads 0.3 mm diameter) for 3 hours to prepare a pigment dispersion. This pigment dispersion was then further subjected to a dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a green pigment dispersion. In Table 1, C.I. I. Pigment Green 36 containing a green pigment dispersion is used as PG36, C.I. I. The case of using a green pigment dispersion containing Pigment Green 7 was designated as PG7.

<Preparation of blue pigment dispersion>
9.54 parts by mass of a blue pigment (CI Pigment Blue 15: 6), 1.06 parts of a pigment derivative shown in Table 1 below, 3.17 parts by mass of a pigment dispersant shown in Table 1 below, PGMEA Was mixed and dispersed in a bead mill (zirconia beads 0.3 mm diameter) for 3 hours to prepare a pigment dispersion. This pigment dispersion was then further subjected to a dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion. In Table 1 below, the case of using this blue pigment dispersion is indicated as PB15: 6.

<Preparation of black pigment dispersion>
A mixed liquid comprising 20.34 parts by mass of a black pigment (titanium black or carbon black), 10.40 parts by mass of a pigment dispersant shown in Table 1 below, and 69.26 parts by mass of PGMEA A pigment dispersion was prepared by mixing and dispersing for 3 hours using (zirconia beads 0.3 mm diameter). This pigment dispersion was then further subjected to a dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a black pigment dispersion. Titanium black was prepared by the method described in paragraph number 0387 of JP2012-150468A. As the carbon black, the one described in paragraph number 0267 of JP2011-203506A was used. In Table 1, the case of using a black pigment dispersion containing titanium black was described as titanium black, and the case of using a black pigment dispersion containing carbon black as carbon black.

<Example of preparation of co-dispersing liquid containing red pigment and black pigment ((B) / total pigment concentration = 0.048)>
7.56 parts by mass of a red pigment, 2.27 parts by mass of a yellow pigment, 0.49 parts by mass of a black pigment, 1.09 parts of a pigment derivative shown in Table 1 below, and a pigment dispersant shown in Table 1 below Was mixed and dispersed with a bead mill (zirconia beads 0.3 mm diameter) for 3 hours to prepare a pigment dispersion. This pigment dispersion was then further subjected to a dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a co-dispersion liquid containing a red pigment and a black pigment.

<Co-dispersing liquid containing red pigment and green pigment, co-dispersing liquid containing red pigment and blue pigment>
In the same manner as described above, a co-dispersion liquid containing a red pigment and a green pigment and a co-dispersion liquid containing a red pigment and a blue pigment were similarly prepared so that the ratios were matched.

<Preparation of photosensitive resin composition (Formulation 1)>
Using the pigment dispersion obtained above, each component was mixed and stirred so as to have the following composition to prepare a photosensitive resin composition.
-Red pigment dispersion 54.63 parts-Black, blue or green dispersion (B) / The amount added was adjusted so that the total pigment concentration was the value shown in Table 1.
For example, (B) / total pigment concentration = 0.048, in the case of black pigment dispersion 1.35 parts. For example, (B) / total pigment concentration = 0.048, in the case of green pigment dispersion 3.07 parts. (B) / total pigment concentration = 0.048, in the case of blue pigment dispersion 2.89 parts · resin (using the one shown in Table 1) 0.61 part · polymerizable compound (KAYARAD RP-1040, Japan 3.10 parts ・ Photopolymerization initiator (OXE-01, manufactured by BASF Corp.) 0.34 parts ・ Surfactant (Megafac F-781, manufactured by DIC Corporation, 0.2%) EEP solution) 4.17 parts · PGMEA 30.91 parts · EEP 4.89 parts · p-methoxyphenol 0.003 parts

<Preparation of photosensitive resin composition (Formulation 2)>
Using the pigment dispersion obtained above, each component was mixed and stirred so as to have the following composition to prepare a photosensitive resin composition.
-Red pigment dispersion containing orange pigment 67.24 parts-Black, blue or green dispersion (B) / The addition amount was adjusted so that the total pigment concentration was the value shown in Table 1.
For example, (B) / total pigment concentration = 0.048, in the case of black pigment dispersion 1.80 parts For example, (B) / total pigment concentration = 0.048, in the case of green pigment dispersion 4.08 parts (B) / total pigment concentration = 0.048, in the case of blue pigment dispersion 3.83 parts · resin (the one described in Table 1) 1.90 parts · polymerizable compound (A-DPH-12E, Shin-Nakamura Chemical Co., Ltd.) 0.56 parts Photopolymerization initiator (OXE-02, manufactured by BASF) 0.80 parts Surfactant (Megafac F-781, manufactured by DIC Corporation) 0% PGMEA solution) 4.17 parts PGMEA 21.26 parts p-methoxyphenol 0.003 parts

<Preparation of photosensitive resin composition (formulation 3) ((B) / total pigment concentration = 0.048)>
Using the pigment dispersion obtained above, each component was mixed and stirred so as to have the following composition to prepare a photosensitive resin composition.
-Co-dispersing liquid 55.98 parts-Resin (using the one listed in Table 1) 0.61 parts-Polymerizable compound (KAYARAD RP-1040, Nippon Kayaku Co., Ltd.) 3.10 parts-Photopolymerization Initiator (OXE-01, manufactured by BASF) 0.34 parts ・ Surfactant (Megafac F-781, manufactured by DIC Corporation, 0.2% EEP solution) 4.17 parts ・ PGMEA 30.91 parts ・EEP 4.89 parts p-methoxyphenol 0.003 parts

Pigment dispersant 3

Pigment dispersant 4

Pigment dispersant 5: Disperbyk 111, manufactured by Big Chemie Japan

Pigment derivative 1

Pigment derivative 2

Pigment derivative 3

Pigment derivative 4

In Table 1 above, (B) / (total pigment) represents (amount of black pigment, green pigment or blue pigment) / (total amount of all pigments) (unit: mass ratio).
(D) Pigment dispersant (for A) indicates the type of pigment dispersant used in the red pigment dispersion, and (D) Pigment dispersant (for B) is a black pigment dispersion or a green pigment dispersion. Or the kind of pigment dispersant used for the blue pigment dispersion is shown. The same applies to pigment derivatives.

<Evaluation>
<< Measurement of spectral transmittance >>
The obtained photosensitive resin composition is applied on a glass wafer (substrate) by spin coating so that the film thickness after application is 1.0 μm, and then heated at 100 ° C. for 2 minutes on a hot plate. did. Furthermore, it heated for 8 minutes at 200 degreeC on the hotplate, and the colored photosensitive resin composition layer was formed.
The spectral transmittance of the substrate on which the colored photosensitive resin composition layer was formed was measured using a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The spectral transmittance at 650 nm is shown in Table 2.

<< Liquid aging at 45 ° C / spectrum after 1 week >>
The photosensitive resin compositions of Examples and Comparative Examples obtained above were aged at 45 ° C. for 1 week, then filtered through a 0.60 μm filter, and the spectral transmittance was measured in the same manner as described above. Further, the difference between the spectral transmittance before the liquid aging and the spectral transmittance after the liquid aging was calculated and evaluated according to the following criteria.
~ Criteria ~
6: Spectral transmittance difference <0.1 point 5: 0.1 point ≦ Spectral transmittance difference <0.5 point 4: 0.5 point ≦ Spectral transmittance difference <1.0 point 3: 1.0 point ≦ Spectral transmittance difference <2.0 points 2: 2.0 points ≦ Spectral transmittance difference <3.0 points 1: 5 points ≦ Spectral transmittance difference

<< Liquid pattern 45 ° C / fine pattern litho residue after 1 week >>
The obtained photosensitive resin composition was aged at 45 ° C. for 1 week, and then applied onto a silicon wafer with an undercoat layer produced as described later using a spin coater so that the film thickness after application was 1.0 μm. It apply | coated and heat-processed (prebaked) for 120 second using the 100 degreeC hotplate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the exposure amount is adjusted so that the pattern size becomes 2.0 μm square through a 2.0 μm square island pattern mask at a wavelength of 365 nm. And exposed.
Thereafter, paddle development was performed on the silicon wafer with the undercoat layer on which the exposed coating film was formed using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 60 seconds. After that, rinsing with a spin shower, further washing with pure water, and heat treatment (post-baking) for 480 seconds using a 200 ° C. hot plate, a monochrome color in which an island pattern of 2.0 μm square is formed. A filter was obtained.
With respect to the obtained 2.0 μm square island pattern, a length measurement SEM (S-4800, manufactured by Hitachi, Ltd.) was used to observe residues around the pattern and evaluated according to the following criteria. In addition, immediately after preparation of the photosensitive resin composition (before liquid aging), no residue was observed even if any photosensitive resin composition was used, and a favorable pattern was formed.
~ Criteria ~
6: No residue is observed.
5: Very little 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.

<< Method for producing silicon wafer with undercoat layer >>
The silicon wafer with the undercoat layer used for evaluation was produced as follows.
On an 8-inch silicon wafer, CT-4000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied by spin coating to form a coating film, and the formed coating film is processed in an oven at 220 ° C. for 1 hour. Then, the coating film was cured to form an undercoat layer. The spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 0.1 μm.

From Table 2 above, it was found that the photosensitive resin composition of Comparative Example, which contains a resin containing an acid group, but the weight average molecular weight of the resin is not 38000 or less, has large spectral fluctuations and more litho residues. . Thus, it turned out that the photosensitive resin composition of a comparative example is inferior to fine pattern resolution.
On the other hand, the photosensitive resin composition of the example having (C) a resin containing an acid group and having a weight average molecular weight of 38000 or less has a small spectral fluctuation (excellent spectral variability), and is more It was found that there was little residue. Thus, it turned out that the photosensitive resin composition of an Example is excellent in fine pattern resolution.

Claims

A colored photosensitive resin composition comprising (A) a pigment, (B) a pigment, (C) a resin having an acid group and a weight average molecular weight of 38000 or less, (D) a pigment dispersant, and (E) a pigment derivative. There,
The (A) pigment comprises at least one selected from a red pigment and an orange pigment, and the mass ratio of the red pigment to the (A) pigment is 0.3 or more,
The (B) pigment comprises at least one selected from a green pigment, a blue pigment and a black pigment,
A colored photosensitive resin composition, wherein a mass ratio of the pigment (B) to the total pigment contained in the colored photosensitive resin composition is 0.005 to 0.25.
The (D) pigment dispersant is
(D-1) A carboxylic acid obtained by reacting a polymer having a hydroxyl group at at least one terminal or a polymer having a primary amino group at at least one terminal with a tricarboxylic acid anhydride or tetracarboxylic dianhydride. Acid dispersants,
(D-2) a phosphoric acid dispersant represented by the following general formula (3):
(D-3) a copolymer containing a structural unit represented by any one of the following general formula (1) and the following general formula (2), and
(D-4) a graft copolymer containing a nitrogen atom in the main chain;
The colored photosensitive resin composition of Claim 1 which is at least 1 sort (s) selected from these.

In the general formula (3), R 3 represents a polyester structure having a number average molecular weight of 400 to 30,000, and y represents 1 or 2. When y is 2, the plurality of R 3 may be the same or different.

In the general formulas (1) and (2), R 1 to R 6 each represent a hydrogen atom or a monovalent organic group,
X 1 and X 2 each represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group,
L 1 and L 2 each represent a single bond or a divalent organic linking group,
A 1 and A 2 each represent a monovalent organic group,
m and n each represents an integer of 2 to 8,
p and q each represents an integer of 1 to 100.
The (E) pigment derivative is
A pigment derivative represented by the general formula (I),
A pigment derivative represented by the general formula (II), and a pigment derivative represented by the general formula (III),
The colored photosensitive resin composition according to claim 1 or 2, which is at least one of the following.

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 —, and Y 2 represents an alkylene group or arylene which may have a substituent. Represents a group,
Y 1 represents —NH— or —O—,
Z represents a hydroxyl group, an alkoxy group, a group represented by the following general formula (I-1), or —NH—X-Dye when n represents 1, and X represents X in the general formula (I) When n represents an integer of 2 to 4, it represents a hydroxyl group, an alkoxy group, or a group represented by the following general formula (I-1),
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.
m represents an integer of 1 to 6, and n represents an integer of 1 to 4.
When n is 2 or more, the plurality of X, Y 1 , R 1 , and R 2 may be the same or different.

In general formula (I-1), 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 may be bonded to each other 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,
X 1 is, -NR'SO 2 -, - SO 2 NR '-, - CONR' -, - CH 2 NR'COCH 2 NR'-, or -NR'CO- represents, X 2 is a substituent An arylene group having 6 to 20 carbon atoms which may have, or a heteroaromatic group having 4 to 20 carbon atoms which may have a substituent, and these groups are represented by —NR′—, They may be bonded to each other through a divalent linking group selected from —O—, —SO 2 —, and —CO—. R ′ has 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 a substituent. And an aryl group having 6 to 20 carbon atoms which may be present.
X 3 represents —NR′— or —O—.

A and B are each a group represented by the following general formula (II-1), a group represented by the following general formula (II-2), —O— (CH 2 ) n —R 8 , —OR 9 , —NR 10 R 11 , —Cl, —F and —X 3 —X 2 —X 1 —Dye, R 8 represents an optionally substituted nitrogen-containing heterocyclic 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, and n represents an integer of 0 to 20.
One of A and B is a group represented by the following general formula (II-1), a group represented by the following general formula (II-2), —O— (CH 2 ) n—R 8 , — OR 9 or —NR 10 R 11 , and t represents an integer of 1 to 3. When t is 2 or more, the plurality of X 1 , X 2 , X 3 , A, and B may be the same or different.

In general formula (II-1), Y 1 represents —NR′— or —O—,
Y 2 may have an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted alkenylene group having 2 to 20 carbon atoms, or an optionally substituted group. And an arylene group having 6 to 20 carbon atoms, and these groups are bonded to each other through a divalent linking group selected from —NR′—, —O—, —SO 2 —, and —CO—. Also good. R ′ has 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 a substituent. And an aryl group having 6 to 20 carbon atoms which may be present.
R 1 and R 2 each 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.
In general formula (II-2), Z 1 is a single bond connecting the triazine ring and the 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 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 substituent Represents an arylene group having 6 to 20 carbon atoms which may have a group, and R ′ and R ″ each represents a hydrogen atom and 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.
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. an alkenyl group having 1-20 or carbon atoms, which may have a substituent or an aryl group of 6 to 20, alkyl group of R 7 is - 1 carbon atoms, which may have a substituent group 20, Alternatively, it represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent.
Formula (III)

In general formula (III), A represents a component capable of forming an azo pigment together with XY.
X represents a single bond or a group selected from divalent linking groups in the following group A.
Y represents a group represented by the following general formula (III-2).
Group A:

In the general formula (III-2), Z represents an alkylene group having 1 to 5 carbon atoms,
R 2 represents an alkyl group having 1 to 4 carbon atoms or a 5- or 6-membered saturated heterocyclic ring containing a nitrogen atom. a represents 1 or 2. * Represents a binding site with X.
The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the (A) pigment contains an orange pigment.
The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the total concentration of all pigments is 30% by mass or more based on the total solid content of the colored photosensitive resin composition.
The content of the resin (C) having an acid group and a weight average molecular weight of 38000 or less is 25% by mass or less based on the total solid content of the colored photosensitive resin composition. The colored photosensitive resin composition of any one of Claims 1.
The pigment (A) is C.I. I. Pigment Red254, C.I. I. Pigment Red177 and C.I. I. The colored photosensitive resin composition according to any one of claims 1 to 6, comprising at least one selected from Pigment Orange 71.
The colored photosensitive resin composition according to any one of claims 1 to 7, further comprising a polymerizable compound having four or more polymerizable groups.
The colored photosensitive resin composition according to any one of claims 1 to 8, further comprising a fluorine-based surfactant.
The colored photosensitive resin composition according to any one of claims 1 to 9, further comprising an oxime polymerization initiator.
The colored photosensitive resin composition according to any one of claims 1 to 10, further comprising a yellow pigment.
The colored photosensitive resin composition according to any one of claims 1 to 11, which is used for forming a colored region of a color filter.
A cured film obtained by curing the colored photosensitive resin composition according to any one of claims 1 to 12.
Applying the colored photosensitive resin composition according to any one of claims 1 to 12 on a support to form a colored photosensitive resin composition layer;
Exposing the colored photosensitive resin composition layer in a pattern;
A step of developing and removing an unexposed portion to form a colored pattern;
A method for producing a color filter comprising:
Applying the colored photosensitive resin composition according to any one of claims 1 to 12 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;
Patterning the photoresist layer by exposure and development to obtain a resist pattern; and dry etching the colored layer using the resist pattern as an etching mask;
A method for producing a color filter, comprising:
A color filter having the cured film according to claim 13.
The color filter manufactured by the manufacturing method of the color filter of Claim 14 or 15.
A solid-state imaging device or an image display device having the color filter according to claim 16 or 17.