TW201506537A - Colored photosensitive resin composition, cured film, color filter, method for manufacturing color filter, solid state image capture device and image display device - Google Patents

Abstract

A colored photosensitive resin composition is provided, which contains a zinc halide phthalocyanine pigment (A), a dye derivative (B-1) represented by the following formula (I) and/or a dye derivative (B-2) represented by the following formula (II), a dispersing agent (C), a photopolymerization initiator (D) and a polymerizable compound (E), wherein the content of the dispersing agent (C) is 20 to 40 parts by mass relative to 100 parts by mass of pigment.

Description

Coloring photosensitive resin composition, cured film, color filter, color Method for manufacturing color filter, solid-state imaging device, and image display device

The invention relates to a liquid crystal display element (Liquid Crystal Display (LCD)) or a solid-state imaging device (Charge-coupled Device (CCD), Complementary Metal Oxide Semiconductor (Complementary Metal- a colored photosensitive resin composition of a color filter used in an Oxide-Semiconductor, CMOS, or the like), a color filter having a colored region formed by the composition, and a color filter having the color filter An image display device such as a solid-state imaging device or a liquid crystal display device for an organic light emitting diode (LED).

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, there is a tendency for liquid crystal displays (LCDs), particularly color liquid crystal displays, to increase. Due to the demand for further high image quality, the popularity of organic electroluminescence (EL) displays is also desired. On the other hand, due to the digital camera, the mobile phone with the camera Popularization, the demand for solid-state imaging elements such as CCD image sensors is also increasing.

As a key device for these displays or optical components, the use of color filters further increases the requirements for higher image quality and cost reduction. Such a color filter usually has a color pattern of three primary colors of red (R), green (G), and blue (B), and functions to divide the passed light into three primary colors in a display element or an image sensor.

As the coloring agent used in the color filter, a pigment is usually used. For example, the coloring composition described in Patent Document 1 to Patent Document 3 has been disclosed.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-156395

[Patent Document 2] Japanese Patent Laid-Open No. 2008-310000

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-251481 (Japanese Patent No. 5117913)

However, although the crosstalk (light mixing) is alleviated by thinning the color filter, it is required to be thinned in a state in which the spectroscopic form is maintained, so that it is required to greatly increase the pigment concentration in the solid component. . Therefore, in the composition described in Patent Document 1 to Patent Document 3, the content of components necessary for lithography is relatively small, and pattern formation tends to be difficult.

Thus, in order to ensure the content of the components necessary for lithography, a small amount of dispersant Obtaining good pigment dispersions has become an important issue.

The present invention solves the above problems, and relates to a colored photosensitive resin composition, a cured film using the colored photosensitive resin composition, a color filter, a method of producing a color filter, a solid-state image sensor, and In the image display device, the colored photosensitive resin composition can obtain a good dispersion with a small amount of a dispersing agent, and has good lithography (resolution), pattern linearity, stability between the same color pixels of the pattern, and Excellent brightness unevenness.

The inventors of the present invention conducted detailed studies and found that the problem can be solved by using a predetermined pigment and a predetermined pigment derivative.

Specifically, the above problem is solved by the following means <1>, preferably means <2>~ means <15>.

<1> A colored photosensitive resin composition containing (A) a zinc halide phthalocyanine pigment, (B-1) a dye derivative represented by the following formula (I), and/or (B-2) a pigment derivative represented by the formula (II), (C) a dispersant, (D) a photopolymerization initiator, and (E) a polymerizable compound, wherein the content of the (C) dispersant is 100 parts by mass based on the pigment 20 parts by mass to 40 parts by mass, [Chemical 1]

(In the general formula (I), Dye represents an n-valent organic dye residue, and X represents a single bond, -CONH-Y ² -, -SO ₂ NH-Y ² - or -CH ₂ NHCOCH ₂ NH-Y ² - ( Y ² represents an alkylene group or an extended aryl group which may have a substituent, and Y ¹ represents -NH- or -O-. When n represents 1, Z represents a hydroxyl group, an alkoxy group, and the following formula (III) a group represented by -NH-X-Dye (X is the same as X in the formula (I)), and when n represents an integer of 2 to 4, Z represents a hydroxyl group, an alkoxy group or The group represented by the following formula (III), R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero ring containing a nitrogen atom; m represents 1 An integer of ~6, n represents an integer of 1 to 4; when n is 2 or more, a plurality of X, Y ¹ , R ¹ and R ² may be the same or different);

(In the formula (III), Y ³ represents -NH- or -O-; R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a nitrogen atom-containing group. Heterocycle; m represents an integer from 1 to 6);

(In the formula (II), Dye represents a quinophthalone residue which may have a substituent, and X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, -CH ₂ NR 'COCH ₂ NR'- or -NR'CO-, X ² represents a aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaromatic ring group having 4 to 20 carbon atoms which may have a substituent, and Some groups may also be bonded to each other via a divalent linking group selected from -NR'-, -O-, -SO ₂ - or -CO-; X ³ represents -NR'- or -O-; R' represents 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 an aryl group having 6 to 20 carbon atoms which may have a substituent; B represents a group represented by the following formula (1), a group represented by the following formula (2), -O-(CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ a group in R ¹¹ , —Cl, —F and —X ³ —X ² —X ¹ —Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, and R ⁹ , R ¹⁰ and R ¹¹ each represent hydrogen. An 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 an aryl group having 6 to 20 carbon atoms which may have a substituent, and n represents 0. An integer of ~20; any of A and B is (1) a group represented by the general formula, the following formula (2) a group represented _{by, -O- (CH 2) n -R} 8, -OR 9 or -NR ¹⁰ R ^11, t represents 1 An integer of ~3; when t is 2 or more, a plurality of X ¹ , X ² , X ³ , A, and B may be the same or different); [Chemical 4]

(In the formula (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, and the carbon number which may have a substituent is 2 to 20 An alkenyl group or a aryl group having 6 to 20 carbon atoms which may have a substituent, and these groups may also be selected from the group consisting of -NR'-, -O-, -SO ₂ -, -CO- The valency linking groups are bonded to each other; R' represents 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 carbon number which may have a substituent An aryl group of 6 to 20; R ¹ and R ² each independently represent 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 Further, a heterocyclic structure may be formed, and the heterocyclic ring structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, or may have a substituent; in the formula (2), Z ¹ represents a linking triazine ring and nitrogen. A single bond of an atom, -NR'-, -NR'-G-CO-, -NR'-G-CONR"-, -NR'-G-SO ₂ -, -NR'-G-SO ₂ NR"- , -OG-CO-, -OG-CONR'-, -OG-SO ₂ - or -OG-SO ₂ NR'-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and may have a substituent having a carbon number of 2 to 20 or an alkenyl group The substituent has a carbon number of 6 to 20, and R' and R" each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent of 2 to 20 An alkenyl group or an aryl group having 6 to 20 carbon atoms which may have a substituent; and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent 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 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 may have The substituent has a carbon number of 2 to 20 alkenyl groups.

<2> The colored photosensitive resin composition as described in <1> further contains a yellow pigment.

<3> The colored photosensitive resin composition as described in <2>, wherein the yellow pigment is a color index (C.I.) Pigment Yellow 150 and/or C.I. Pigment Yellow 185.

The coloring photosensitive resin composition as described in any one of <1> to <3> wherein the (C) dispersing agent is the hydroxyl group and tricarboxylic acid of the vinyl polymer which has a hydroxyl group in a single terminal. An acid anhydride or a tetracarboxylic dianhydride is reacted.

The colored photosensitive resin composition according to any one of <1> to <4>, wherein, in the formula (I), Dye has a monoazo dye structure containing a benzimidazolone skeleton.

The colored photosensitive resin composition as described in any one of <1> to <5>, wherein, in the formula (II), the quinophthalone residue is represented by the following formula (II-1) Said that

In the formula (II-1), D and E each represent an aromatic group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring bonded to D and E, and a substituent. a cyclic or heterocyclic group, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a carboxyl group or a salt thereof, an ester group having 1 to 20 carbon atoms, a decylamino group having 1 to 20 carbon atoms, an anthracenyl group or a salt thereof, and an amine Any one of a sulfonyl group, a -NR'R"-, or a nitro group; wherein R' and R" each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and may have a substituent The alkenyl group having 2 to 20 carbon atoms or the aryl group having 6 to 20 carbon atoms which may have a substituent; p represents an integer of 0 to 4, q represents an integer calculated by 4-p; * represents a formula The bonding site of X ¹ in II).

The colored photosensitive resin composition as described in any one of <1> to <6>, wherein A and B in the formula (II) represent a group or a formula represented by the formula (1). (2) The group represented, and A and B are the same group.

The colored photosensitive resin composition as described in any one of <1> to <7>, wherein (A) the zinc halide phthalocyanine pigment is C.I. Pigment Green 58.

The colored photosensitive resin composition as described in any one of the above-mentioned items, wherein the total amount of the coloring agent is 40% by mass or more based on the total solid content in the composition.

<10> The colored photosensitive resin composition according to any one of <1> to <9> which is a colored region for forming a color filter.

<11> A cured film obtained by curing the colored photosensitive resin composition according to any one of <1> to <10>.

<12> A method of manufacturing a color filter, comprising the steps of: The coloring photosensitive resin composition according to any one of the items 1 to 10, which is applied to a support to form a colored photosensitive resin composition layer; and the step of exposing the colored photosensitive resin composition layer to a pattern And a step of developing the colored pattern by developing the unexposed portion.

<13> A method of producing a color filter, comprising the step of applying a colored photosensitive resin composition according to any one of <1> to <10> to a support to form a colored photosensitive resin composition. a step of hardening the layer to form a color layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and a resist The agent pattern serves as an etching mask to dry etch the colored layer.

<14> A color filter which is a color filter having a cured film according to <11> or a method of producing a color filter according to <12> or <13>. Color filter.

<15> A solid-state imaging device or image display device comprising the color filter according to <14>.

According to the present invention, even if the content of the dispersant is small, a good dispersion can be obtained, so that a good lithography (analytical property), pattern linearity, stability between the same color pixels of the pattern, and excellent unevenness in brightness can be provided. a coloring photosensitive resin composition, a cured film using the colored photosensitive resin composition, a color filter, and a color filter A method of manufacturing a light sheet, a solid-state image sensor, and an image display device.

FIG. 1 is a view schematically showing a criterion for judging the evaluation of pattern linearity.

Hereinafter, the contents of the present invention will be described in detail. In addition, in the specification of the present application, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit. Further, the organic EL device of the present invention means an organic electroluminescence device.

In the present specification, the total solid content refers to the total mass of the components obtained by removing the solvent from the total composition of the colored photosensitive resin composition.

In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes a group having no substituent, and also includes a group having 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, the term "radiation" as used herein means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV) light, an X ray, an electron beam, or the like. Further, the term "light" as used in the present invention means actinic ray or radiation. In the present specification, the term "exposure" is used to describe not only the ultraviolet light, the X-ray, the EUV light, etc., which are represented by mercury lamps or excimer lasers, but also the use of particle beams such as electron beams and ion beams. Also included in the exposure.

In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid," The (meth)acrylonyl group means either or both of an acryloyl group and a methacryl group.

In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present specification means a compound which is distinguished from an oligomer and a polymer and has 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 the present specification, the weight average molecular weight and the number average molecular weight are defined by polystyrene-converted values obtained by GPC measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using TSKgel Super AWM-H (Dongcao) As a column, a 10 mmol/L solution of lithium bromide N-methylpyrrolidone (NMP) was used as a solution.

In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

The term "step" in this specification refers not only to an independent step, but also to a situation where it cannot be clearly distinguished from other steps, as long as the intended effect of the step can be achieved.

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

<Coloring photosensitive resin composition>

The colored photosensitive resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention" or "colored composition") is characterized by containing (A) a zinc halide phthalocyanine pigment and (B-1) (I) a pigment derivative and/or (B-2) a dye derivative represented by the formula (II) (hereinafter collectively referred to as "(B) pigment derivative"), (C) a dispersant, (D) Photopolymerization initiator and (E) polymerizable compound, the content of the (C) dispersant is 20 parts by mass to 40 parts by mass based on 100 parts by mass of the total amount of the pigment.

By using the composition of the present invention, even if the content of the dispersant is as small as 20 parts by mass to 40 parts by mass relative to 100 parts by mass of the pigment, a good dispersion can be obtained, so that good lithography (analytical property) is obtained. The linearity of the pattern, the stability of the same color of the pattern, and the unevenness in brightness are excellent. Although the reason why the effect of the present invention can be obtained is not certain, it is considered to be because the plane of the molecular structure of the zinc halide phthalocyanine used as a pigment is compared with that of a non-halogenated phthalocyanine or copper phthalocyanine. More sexual. In other words, it is considered that when the pigment is dispersed by the interaction of the dispersant, the higher the planarity of the molecule, the easier the adsorption is. Therefore, it is also possible to disperse with a small amount of the dispersant.

Further, the (B) dye derivative used in the present invention has a triazine structure, and the triazine structure and the highly planar compound strongly adsorb, so that the highly planar zinc halide phthalocyanine is more strongly adsorbed to the dye derivative. . It can be speculated that for these reasons, even points A small dispersion can also provide a good dispersion.

Hereinafter, the composition of the present invention will be described in detail.

<<(A) Zinc Halogen Phthalocyanine Pigment>>

The present invention contains (A) a zinc halide phthalocyanine pigment. The zinc halide phthalocyanine pigment of the present invention is a pigment having a structure in which a substituent substituted on a phthalocyanine skeleton is only a halogen atom, and a total of at least 2 and a maximum of 16 are bonded to each phthalocyanine molecule (structure). Halogen atom.

The halogen atom preferably contains at least one selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom, more preferably a chlorine atom and/or a bromine atom, and further preferably contains both a chlorine atom and a bromine atom.

The zinc halide phthalocyanine pigment may, for example, be a compound represented by the following formula (F).

(In the formula (F), X ¹ to X ¹⁶ each represent a chlorine atom, a bromine atom or a hydrogen atom, and at least two of X ¹ to X ¹⁶ are a chlorine atom or a bromine atom)

When the number of bonded halogen atoms in the molecule increases, the hue of the zinc halide phthalocyanine pigment changes from blue to green. In order to make the zinc halide phthalocyanine pigment green, it is preferable to have 8 or more bromine atoms as a halogen atom bonded to a molecule, and it is preferable to further exhibit a yellow color with a high luminance. It has 12 or more bromine atoms. In terms of further obtaining a yellowish green color, it is preferred to contain more bromine atoms than the chlorine atom.

Among them, 8 or more of X ¹ to X ¹⁶ are substituted with a bromine atom to exhibit a green color having a high luminance, so that it can be preferably used for a green pixel (coloring pattern) of a color filter, and the substitution number of a bromine atom is more Good for 10~14. Further, it is preferable that two or less hydrogen atoms are taken from X ¹ to X ¹⁶ .

The zinc halide phthalocyanine pigment used in the present invention is preferably a zinc halide phthalocyanine having an average particle diameter of primary particles of from 0.01 μm to 0.30 μm. The average particle diameter of the primary particles of the pigment in the present invention is a value measured by the method shown below.

The average primary particle diameter of the present invention means a value of a particle in a visual field by a transmission electron microscope, and 100 of a zinc halide phthalocyanine pigment constituting an aggregate on a two-dimensional image. The primary particles are each obtained by averaging the average values of the longer particle diameter (long diameter) and the shorter particle diameter (short diameter), and averaging the values.

In the composition of the present invention, the zinc halide phthalocyanine pigment may be used singly or in combination of two or more. For example, in the above formula (F), a plurality of specificities in which the number of substitutions of a halogen atom selected from a bromine atom and a chlorine atom are different from each other in a specific ratio can also be used. A polyhalogenated zinc phthalocyanine pigment composed of a halogen atom.

Preferable examples thereof include a polyhalide zinc phthalocyanine pigment containing 16 bromine atoms, a combination with a polyhalogenated zinc phthalocyanine pigment containing 15 bromine atoms and 1 chlorine atom, and the like. In addition, the ratio of the two is preferably in the range of 80:20 to 100:0.

The average composition of the (A) zinc halide phthalocyanine pigment contained in the curable composition of the present invention is determined by mass spectrometry based on mass spectrometry and halogen content analysis by flask combustion ion chromatography, and halogenated. The percentage of mol% (mol%) of each specific zinc halide phthalocyanine pigment in the zinc phthalocyanine pigment composition can also be easily determined by analyzing the results of the mass analysis.

The zinc halide phthalocyanine pigment which can be preferably used in the present invention can be produced by the method described in JP-A-2007-320986 and JP-A-2008-19383.

The zinc halide phthalocyanine pigment is exemplified by C.I. Pigment Green 58.

The amount of the zinc halide phthalocyanine pigment in the composition of the present invention is preferably from 20% by mass to 100% by mass, more preferably from 30% by mass to 90% by mass, even more preferably from 40% by mass to 80% by mass, based on all the pigment components. .

-Other pigments -

The composition of the present invention may also contain other pigments other than the zinc halide phthalocyanine pigment. Specifically, it can be described in Paragraph No. 0046 to Paragraph No. 0052 of JP-A-2012-219106, which is incorporated herein by reference. In the present invention, a yellow pigment is preferred. Other pigments may be used alone or in combination of two or more.

Examples of the organic pigment include an azo pigment, an azomethine pigment, an isoporphyrin pigment, a quinophthalone pigment, and the like. Among them, azo pigments and isoporphyrin pigments are preferred because of dispersion stability, and specific examples thereof include CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, and CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 199, and the like.

Among these, C.I. Pigment Yellow 150 (azo pigment), C.I. Pigment Yellow 139, C.I. Pigment Yellow 185 (isoporphyrin pigment) are preferred.

The other pigments used in the present invention preferably have one or two ring structures in the molecules constituting the other pigments. Here, regarding the condensed ring, the entire condensed ring is regarded as one ring structure.

It is considered that the pigment having a ring structure of three or more pigments has a small intermolecular interaction of one or two pigments, so that the pigment is easily released when dispersed (microparticles). In addition, when the number of particles is increased by the release of the pigment, it is easy to cause adsorption of the zinc halide phthalocyanine pigment, and re-agglomeration of the phthalocyanine having strong cohesive force is suppressed, so that coarse particles contributing to uneven brightness are obtained. Or the effect of viscosity stability (inhibition of viscosity increase) is effective. The pigment having one or two ring structures in the molecule constituting the pigment is preferably a yellow pigment, more preferably C.I. Pigment Yellow 150, C.I. Pigment Yellow 185.

The composition of the present invention may also contain a known dye other than the pigment (A). For example, Japanese Patent Laid-Open Publication No. Sho 64-90403, Japanese Patent Laid-Open No. Hei 64-91102, Japanese Patent Laid-Open No. Hei No. Hei 1-94301, Japanese Patent Laid-Open No. Hei 6-11614, Japanese Patent Registration No. 2592207 , U.S. Patent No. 4,808, 510, U.S. Patent No. 5,679, 920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 505, 950, Japanese Patent Laid-Open No. Hei No. Hei 5- 333 207, Japanese Patent Laid-Open No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-51115, Japan The pigment disclosed in Japanese Laid-Open Patent Publication No. Hei 6-194928 or the like. The chemical structure can be used: pyrazo azo, pyrromethylene, aniline azo, triphenylmethane, lanthanide, benzylidene, oxonium, pyrazolotriazole A dye such as an azo type, a pyridone azo type, a cyanine type, a phenothiazine type, or a pyrrolopyrazole-imine type.

Further, a dye polymer can also be used as the dye. The compound described in Japanese Laid-Open Patent Publication No. 2011-041097, and the Japanese Patent Publication No. 2013-041097.

The content of the pigment in the composition of the present invention is preferably 40% by mass or more based on the total amount of the phthalocyanine pigment and the other pigment, based on the total amount of the phthalocyanine pigment and other pigments, which are contained in the coloring photosensitive resin composition. More preferably, it is 45 mass% - 70 mass%, and further preferably 50 mass% - 65 mass%. The composition of the present invention may contain a dye in a range not departing from the gist of the present invention, and in the case of containing a dye, it is preferred that the total amount of the colorant (dye and pigment) is within the above range.

The pigment may be contained in the composition of the present invention alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

<<(B) Pigment Derivatives>>

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

- (B-1) a pigment derivative represented by the formula (I) -

(In the general formula (I), Dye represents an n-valent organic dye residue, and X represents a single bond, -CONH-Y ² -, -SO ₂ NH-Y ² - or -CH ₂ NHCOCH ₂ NH-Y ² - ( Y ² represents an alkylene group or an extended aryl group which may have a substituent, and Y ¹ represents -NH- or -O-. When n represents 1, Z represents a hydroxyl group, an alkoxy group, and the following formula (III) a group represented by -NH-X-Dye (X is the same as X in the formula (I)), and when n represents an integer of 2 to 4, Z represents a hydroxyl group, an alkoxy group or In the group represented by the following formula (III), R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero ring containing a nitrogen atom. m represents 1 An integer of ~6, and n represents an integer of 1 to 4. When n is 2 or more, a plurality of X, Y ¹ , R ^{1 ,} and R ² may be the same or different)

(In the formula (III), Y ³ represents -NH- or -O-. R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a nitrogen atom-containing group. Heterocycle. m represents an integer from 1 to 6)

Dye represents an n-valent organic pigment residue. The organic dye residue may, for example, be a chromogenic atomic group in the pigment as described above, a similar structure or a partial structure thereof, and specifically includes a skeleton selected from the group consisting of a skeleton having an azo group, a skeleton having a urea structure, and a skeleton having a mercapto structure. a structure having a cyclic guanamine structure, an aromatic ring having a 5-membered ring containing a hetero atom, and a partial structure having one or more aromatic rings having a 6-membered ring containing a hetero atom, and Dye contains the structure. Substituents for some organic pigment residues.

Dye preferably has a pigment core structure or a pigment core structure and an aromatic ring, or a nitrogen-containing aromatic ring, or an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring, and the amine group is bonded to the pigment directly or through a linking group. Any of a core structure, an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring. Specific examples thereof include a quinoline-based residue, a benzimidazolone-based residue, an isoporphyrin-based residue, a diketopyrrolopyrrole-based residue, an azo-based residue, a phthalocyanine-based residue, and an anthracene. Residue, quinacridone residue, dioxin-based residue, piperidone-based residue, lanthanide residue, thioindole residue, isoindolinone residue, quinacridone Residues, threne residues, metal complex residues, and the like.

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

[化12]

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

X represents a single bond, -CONH-Y ² -, -SO ₂ NH-Y ² - or -CH ₂ NHCOCH ₂ NH-Y ² -, preferably a single bond.

Y ² represents an alkylene group or an extended aryl 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 more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples thereof include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The alkylene group may have a substituent, and the substituent may be a group described in the item of the substituent.

The aryl group is preferably a aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include a stretching phenyl group, a stretching naphthyl group, and a stretching group.

The alkylene group and the extended aryl group may have a substituent, and the substituent may be a group described in the item of the substituent.

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

R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero ring containing a nitrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof 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, a n-hexyl group, and an n-octyl group. The alkyl group may have a substituent, and the substituent may be a group described in the item of the substituent.

R ¹ and R ² preferably represent the same alkyl group which may have a substituent.

m represents an integer of 1 to 6, preferably 1 to 4, more preferably 1 to 3.

n represents an integer of 1 to 4, preferably 1 to 3, more preferably 1 or 2.

In the case where n represents 1, the Z represents a hydroxyl group, an alkoxy group, a group represented by the above formula (III) or -NH-X-Dye (X has the same meaning as X in the formula (I)) In the case where n represents an integer of 2 to 4, Z represents a hydroxyl group, an alkoxy group or a group represented by the above formula (III).

In the case where n represents 1, Z is preferably a group represented by the above formula (III) or -NH-X-Dye, more preferably a group represented by the above formula (III).

When n represents an integer of 2 to 4, Z is preferably a group represented by the above formula (III).

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

R ¹ and R ² in the formula (III) each represent an alkyl group which may have a substituent, and have the same meanings as R ¹ and R ² in the formula (I), and the preferred range is also the same. R ¹ and R ² in the formula (III) are preferably an alkyl group which may have the same substituent. Further, R ¹ and R ² in the formula (III) are preferably an alkyl group which may have the same substituent as R ¹ and R ² in the formula (I).

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

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

[Chemistry 14]

[化15]

[化17]

[Chemistry 19]

[Chem. 24]

[Chem. 26]

- (B-2) a pigment derivative represented by the formula (II) -

General formula (II)

In (Formula (II), Dye represents quinophthalone residue having a substituent, X ¹ represents _{-NR'SO 2 -, - SO 2 NR} '-, - CONR' -, - CH 2 NR'COCH 2 NR'- or -NR'CO-, X ² represents a aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaromatic ring group having 4 to 20 carbon atoms which may have a substituent, and these groups It may also be bonded to each other via a divalent linking group selected from -NR'-, -O-, -SO ₂ - or -CO-. X ³ represents -NR'- or -O-. R' represents 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 an aryl group having 6 to 20 carbon atoms which may have a substituent. A and B respectively represent a group represented by the following formula (1), a group represented by the following formula (2), -O-(CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ¹¹ , a group in -Cl, -F and -X ³ -X ² -X ¹ -Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, and R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom; The alkyl group having 1 to 20 carbon atoms having a substituent, 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, and n representing 0 to 20 An integer. Any one of A and B is the following general formula (1) A group represented by the following general formula (2) a group represented _{by, -O- (CH 2) n -R} 8, -OR 9 or -NR ¹⁰ R ^11, t represents an integer of 1 to 3 at t In the case of 2 or more, a plurality of X ¹ , X ² , X ³ , A, and B may be the same or different)

(In the formula (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, and the carbon number which may have a substituent is 2 to 20 An alkenyl group or a aryl group having 6 to 20 carbon atoms which may have a substituent, and these groups may also be selected from the group consisting of -NR'-, -O-, -SO ₂ -, -CO- The valency linking groups are bonded to each other. R' represents 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 carbon number which may have a substituent An aryl group of 6 to 20. R ¹ and R ² each independently represent 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 The heterocyclic structure may be formed integrally, and the heterocyclic ring structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, or may have a substituent.

In the formula (2), Z ¹ represents a single bond linking a triazine ring to a nitrogen atom, -NR'-, -NR'-G-CO-, -NR'-G-CONR"-, -NR'-G _{-SO 2 -, - NR'-G} -SO 2 NR "-, - OG-CO -, - OG-CONR '-, - OG-SO 2 - or _{-OG-SO 2 NR' -,} G represents an The substituent has an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an exoaryl group having 6 to 20 carbon atoms which may have a substituent, R' and R "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 an aryl group having 6 to 20 carbon atoms which may have a substituent R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent 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 may have a substitution. The carbon number of the group is 6 to 20 aryl groups, and 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)

In the formula (II), Dye represents a quinacridone residue which may have a substituent. The quinophthalone residue is specifically represented by the following formula (II-1).

(In the formula (II-1), D and E each represent a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring bonded to D and E, and may have a substituent. An aromatic ring group or a heterocyclic group, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a carboxyl group or a salt thereof, an ester group having 1 to 20 carbon atoms, a decylamino group having 1 to 20 carbon atoms, a fluorenyl group or a salt thereof, Any one of an aminesulfonyl group, a -NR'R"-, and a nitro group. In the formula, R' and R" each independently represent a hydrogen atom, a C1-C20 alkyl group which may have a substituent, and may have The alkenyl group having 2 to 20 carbon atoms of the substituent or the aryl group having 6 to 20 carbon atoms which may have a substituent. p represents an integer of 0 to 4, and q represents an integer calculated by 4-p. * represents a general formula The bonding site of X ¹ in (II)

D and E each represent an aromatic ring group or a heterocyclic group, a hydroxyl group which is selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring bonded to D and E, and which may have a substituent. Alkoxy group having 1 to 3 carbon atoms (for example, methoxy group, ethoxy group, or propoxy group), carboxyl group or salt thereof, ester group having 1 to 20 carbon atoms, decylamino group having 1 to 20 carbon atoms, or fluorenyl group Or a salt thereof, an aminesulfonyl group, a -NR'R"-, or a nitro group. R' and R" each independently represent a hydrogen atom, a C1-C20 alkyl group which may have a substituent, The alkenyl group having 2 to 20 carbon atoms having a substituent or an aryl group having 6 to 20 carbon atoms which may have a substituent.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof 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, a 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 ring group or heterocyclic group represented by D and E, the alkyl group having 1 to 20 carbon atoms represented by R' and R", the alkenyl group having 2 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may also be used. Have taken The substituent, the substituent may be exemplified by the group described in the item of the substituent.

Among these groups, D and E are preferably a hydrogen atom or a halogen atom.

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

The bonding site with X ¹ in the formula (II) is not particularly limited, and it is preferred that the 5-position or the 8-position of the quinoline skeleton in the quinophthalone residue is a bonding site, and more preferably the 8-position is a bond. Knot part.

In the general formula (II), X ¹ represents _{-NR'SO 2 -, - SO 2 NR} '-, - CONR' -, - CH 2 NR'COCH 2 NR'- or -NR'CO-, preferably - NR'SO ₂ -. Furthermore, when t is 2 or more, a plurality of X ¹ may be the same or different.

R' in the above X ¹ represents 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 carbon number which may have a substituent The 6 to 20 aryl group is preferably a hydrogen atom.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof 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, a 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, more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples thereof include a vinyl 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 thereof include a phenyl group, a naphthyl group, an anthracenyl group and the like.

These groups may also have a substituent, and the substituent may be exemplified by the group described in the item of the substituent.

In the formula (II), X ² represents a aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaromatic ring group having 4 to 20 carbon atoms which may have a substituent, and these groups may also be The divalent linking groups selected from -NR'-, -O-, -SO ₂ - or -CO- are bonded to each other (R' has the same meaning as R' in the X ¹ , and the preferred range is also the same) . Further, when t is 2 or more, a plurality of X ² may be the same or different.

The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, and an anthracene group.

The heteroaromatic ring group having 4 to 20 carbon atoms is preferably a heteroaromatic ring group having 4 to 10 carbon atoms, and specific examples thereof include a thiophene ring group, a pyridine ring group, and a pyrrole ring group.

These groups may also have a substituent, and the substituent may be exemplified by the group described in the item of the substituent.

X ³ represents -NR'- or -O-, preferably -NR'-. Further, when t is 2 or more, a plurality of X ³ may be the same or different. R' has the same meaning as the R', and the preferred range is also the same.

A and B respectively represent a group selected from the following general formula (1) or the following general formula (2), -O-(CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ¹¹ , a group in -Cl, -F or -X ³ -X ² -X ¹ -Dye, any of A and B being a group represented by the following formula (1) or formula (2), -O -(CH ₂ ) _n -R ⁸ , -OR ⁹ or -NR ¹⁰ R ¹¹ . In particular, both A and B are preferably a group represented by the following formula (1) or the following formula (2), and more preferably A and B are the following formula (1) or the following formula ( 2) The group represented, and A and B are the same group.

R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, and specific examples thereof include a pyrrole ring residue, a pyridine ring residue and the like.

R ⁹ , R ¹⁰ and R ¹¹ each independently represent 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 carbon number which may have a substituent It is an aryl group of 6-20. R ⁹ , R ¹⁰ and R ¹¹ have the same meanings as R', and the preferred ranges are also the same.

General formula (1)

(In the formula (1), Y ¹ represents -NR'- or -O-, and Y ² represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, and the carbon number which may have a substituent is 2 to 20 An alkenyl group or a aryl group having 6 to 20 carbon atoms which may have a substituent, and these groups may also be selected from the group consisting of -NR'-, -O-, -SO ₂ -, -CO- The valency linking groups are bonded to each other. R' represents 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 carbon number which may have a substituent Is an aryl group of 6 to 20. R ¹ and R ² each independently represent 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 also be integrated to form a heterocyclic structure, which may further contain a nitrogen atom, an oxygen atom or a sulfur atom, or may have a substituent))

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

Y ² represents an alkylene 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 an exoaryl group having 6 to 20 carbon atoms which may have a substituent. The groups may also be bonded to each other via a divalent linking group selected from the group consisting of -NR'-, -O-, -SO ₂ -, -CO- (R' has the same meaning as the R', preferably The scope is 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 more preferably an alkylene group having 1 to 3 carbon atoms. . Specific examples thereof include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The alkylene group may have a substituent, and the substituent may be a group described in the item of the substituent.

The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 to 3 carbon atoms. . Specific examples thereof include an ethynyl group, a propylene group, a butenyl group, a pentenyl group, and a hexenylene group. The alkenyl group may have a substituent, and the substituent may be a group described in the item of the substituent.

The extended aryl group having 6 to 20 carbon atoms is preferably an extended aryl group having 6 to 20 carbon atoms, more preferably an extended aryl group having 6 to 10 carbon atoms. Specific examples thereof include a stretching phenyl group, a stretching naphthyl group, and a stretching group. The extended aryl group may have a substituent, and the substituent may be exemplified by the group described in the item of the substituent.

R ¹ and R ² each independently represent 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 integrally formed). The heterocyclic structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, and may have a substituent.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof 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, a 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, more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.

These groups may also have a substituent, and the substituent may be exemplified by the group described in the item of the substituent. R ¹ and R ² preferably represent the same group.

General formula (2)

(In the formula (2), Z ¹ represents a single bond linking a triazine ring to a nitrogen atom, -NR'-, -NR'-G-CO-, -NR'-G-CONR"-, -NR'- _{G-SO 2 -, - NR'} -G-SO 2 NR "-, - OG-CO -, - OG-CONR '-, - OG-SO 2 - or _{-OG-SO 2 NR' -,} G represents a substituted 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 an exoaryl group having 6 to 20 carbon atoms which may have a substituent, R' and R" each represents 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 an aromatic group having 6 to 20 carbon atoms which may have a substituent. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent 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 may have The substituent has an aryl group having 6 to 20 carbon atoms, and 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)

Z ¹ represents a single bond linking a triazine ring to a nitrogen atom, -NR'-, -NR'-G-CO-, -NR'-G-CONR"-, -NR'-G-SO ₂ -, -NR _{'-G-SO 2 NR "-} , - OG-CO -, - OG-CONR' -, - OG-SO 2 - or -OG-SO ₂ NR'-, preferably a single bond.

R' and R" each represent 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 carbon number which may have a substituent of 6 to 6 The aryl group of 20, R' and R" have the same meanings as R' in the formula (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 alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an exoaryl group having 6 to 20 carbon atoms which may have a substituent. G has the same meaning as Y ² in the formula (1), and the preferred range is also the same.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent 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 may have a substituent The carbon number is 6 to 20 aryl groups. R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as R' in the formula (1), and the preferred range is 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 the formula (1), and the preferred range is also the same.

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

Specific examples of the dye derivative represented by the formula (II) used in the present invention are shown below, but the present invention is not limited to these specific examples.

[化34]

[化35]

[化36]

The content of the (B) dye derivative of the present invention is preferably 0.5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the total of the phthalocyanine pigment and the other pigments. More preferably, it is 1 mass part or more and 25 mass parts or less.

The pigment derivative may be contained alone or in combination of two or more kinds in the composition of the present invention. When two or more cases are contained, it is preferable that the total amount is the said range.

<<(C) Dispersant>>

The composition of the present invention contains (C) a dispersant, and the content of the dispersant is from 20 parts by mass to 40 parts by mass based on 100 parts by mass of the pigment. In the present invention, even if the content of the dispersant is small, a good dispersion can be obtained, so that it has excellent lithography (analytical properties), pattern linearity, stability between the same color pixels of the pattern, and excellent luminance unevenness. The content of the (C) dispersant of the present invention is preferably from 22 parts by mass to 38 parts by mass, more preferably from 25 parts by mass to 35 parts by mass, per 100 parts by mass of the total of the phthalocyanine pigment and the other pigment.

The dispersing agent may be contained in the composition of the present invention alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

The dispersing agent which can be used in the present invention is exemplified by a polymer dispersing agent [for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, and a modification. Polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, fumarate naphthalenesulfonate condensate], and polyoxyalkylene alkyl phosphate, polyoxyethylene ethyl Surfactants such as amines and alkanolamines, pigment derivatives, and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure thereof.

High end-modification type with an anchor portion to the surface of the pigment For example, the polymer having a phosphate group at the terminal described in Japanese Patent Laid-Open No. Hei. No. Hei. No. 2002-273191, and the like. A polymer having a partial skeleton or a heterocyclic ring of an organic dye described in Japanese Laid-Open Patent Publication No. Hei 9-77994, and the like. In addition, two or more fixed sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic groups, etc.) on the surface of the pigment are introduced into the polymer terminal as described in JP-A-2007-277514. The polymer also has excellent dispersion stability and is preferred.

The graft-type polymer having a fixed portion on the surface of the pigment is, for example, a polyester-based dispersant, and the like, and a Japanese Patent Laid-Open Publication No. Hei 54-37082, Japanese Patent Publication No. Hei 8-507960, and Japan The reaction product of a poly(lower alkylene imine) and a polyester described in JP-A-2009-258668, and the like, and polyallylamine and polyester described in JP-A-9-169821. a copolymer of a macromonomer and a nitrogen atom monomer described in Japanese Patent Laid-Open No. Hei 10-339949, Japanese Patent Laid-Open No. Hei No. 2004-37986, and International Publication No. WO2010/110491, Japanese Patent Laid-Open No. 2003 A graft-type polymer having a partial skeleton or a heterocyclic ring of an organic dye described in Japanese Laid-Open Patent Publication No. 2008-81732, and the like. A copolymer of a macromonomer and an acid group-containing monomer described in Japanese Patent Publication No. 106268 or the like. In particular, in view of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored photosensitive resin composition using the pigment dispersion, it is described in Japanese Patent Laid-Open Publication No. 2009-203462. Alkaline base An acidic amphoteric dispersion resin.

A known macromonomer can be used as the macromonomer used for the production of the graft-type polymer having a fixed portion on the surface of the pigment by radical polymerization, and examples thereof include a macromonomer AA-6 manufactured by East Asia Synthetic Co., Ltd. (polymethyl methacrylate with terminal group being methacryl fluorenyl), AS-6 (polystyrene with terminal group of methacryl fluorenyl), AN-6S (benzene with terminal group of methacryl fluorenyl) Copolymer of ethylene and acrylonitrile), AB-6 (polybutyl acrylate of methacryl fluorenyl group), Placcel FM5 manufactured by Daicel Chemical Industry Co., Ltd. 2-hydroxyethyl acrylate ε-caprolactone 5 molar equivalent plus finished product), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10 molar equivalent plus finished product), and Japanese Patent Laid-Open 2- The polyester-based macromonomer described in the publication No. 272009. Among these monomers, in particular, from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the colored photosensitive resin composition using the pigment dispersion, it is particularly preferable that it is soft and solvophilic. The polyester-based macromonomer which is excellent in the polyester-based macromonomer described in JP-A No. 2-272009.

The block type polymer which has a fixed part to the surface of the pigment is preferably a block type polymer described in JP-A-2003-49110, JP-A-2009-52010, and the like.

The dispersing agent which can be used in the present invention can also be obtained as a commercially available product, and specific examples thereof include "DA-7301" manufactured by Nanmu Chemical Co., Ltd.; "Diss manufactured by BYK Chemie" Disperbyk-101 (polyamine-amine phosphate), Disperbyk-107 (carboxylate), Disperbyk-110 (acid-containing copolymer), Disperbyk-130 (polyamide), Disperbyk-161, Dispabbi Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166 , Disperbyk-170 (polymer copolymer), "BYK-P104, BYK P105 (high molecular weight unsaturated polycarboxylic acid)"; EFKA EFKA 4047, EFKA 4050~EFKA 4010~Efka 4165 (polyurethane), Evka (made by the company) EFKA) 4330~Evka (EFKA) 4340 (block copolymer), Efka (EFKA) 4400~Evka (EFKA) 4402 (modified polyacrylate), Efka (EFKA) 5010 (polymerized) Esteramide), Efka (EFKA) 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 (fatty acid polyester), Efka (EFKA) 6745 (phthalocyanine derivative), Eve Card (EFKA) 6750 (azo pigment derivative)"; Ajisper PB821, Aji by Ajinomoto Fine-Techno Ajisper PB822, Ajisper PB880, Ajisper PB881"; Flowlen TG-710 (urethane oligosaccharide) manufactured by Kyoeisha Chemical Co., Ltd. "Polymer", "Polyflow No. 50E, Polyflow No. 300 (acrylic copolymer)"; "Disperlon KS" manufactured by Nanben Chemical Co., Ltd. 860, Disperlon 873SN, Disperlon 874, Disperlon #2150 (aliphatic polycarboxylic acid), Disperlon #7004 (polyether ester) ), Disparon (Disperlon) DA-703-50, Disperlon DA-705, Disperlon DA-725"; Demol RN, Demol (made by Kao) N) (formalin desulfonate polycondensate), Demol MS, Demol C, Demol SN-B (aromatic sulfonate polycondensate), Fire Momogenol L-18 (polymer polycarboxylic acid), "Emulgen 920, Emulgen 930, Emulgen 935, Emulgen 985 (polyoxygen) "Ethyl decyl phenyl ether", "Acetamine 86 (stearylamine acetate)"; "Sonupas (made by Lubrizol Japan) Solsperse) 5000 (phthalocyanine derivative), Solsperse 22000 (azo pigment derivative), Solsperse 13240 (polyesteramine), Solsperse 3000, cable Solsperse 17000, Solsperse 27000 (polymer with functional part at the end), Solsperse 24000, Solsperse 28000, Sonupas (Solsperse) 32000, Solsperse 38500 (grafted polymer) "Nikkol T106 (polyoxyethylene ethyl sorbitan monooleate) manufactured by Nikko Chemical Co., Ltd., Nikkol MYS-IEX (polyoxyethylidene monostearate)"; Hinoact T-8000E manufactured by Chuanyan Refinery Co., Ltd.; organic siloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.; "W001: Cationic interface activity" manufactured by Yushang Co., Ltd. Agent, polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethylene decyl benzene Ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fat Non-ionic surfactants such as acid esters, anionic surfactants such as "W004, W005, W017"; "EFKA-46" and EFKA-47 manufactured by Morishita Industries Co., Ltd. EFKA-47EA, Efka (EFKA) polymer 100, Efka (EFKA) polymer 400, Efka (EFKA) polymer 401, Efka (EFKA) polymer 450"; Disperse-aid 6, Disperse-aid 8, Disperse-aid 15, made by Sannopco A polymer dispersant such as Disperse-aid 9100; Adeka Pluronic L31 and Adeka Pluronic F38 made by ADEKA , Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Eddie Pronick (Adeka Pluronic) F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adi Copronik (Ade Ka Pluronic) P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Ai Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123"; and Ionet manufactured by Sanyo Chemicals Co., Ltd. ) (trade name) S-20" and so on.

These dispersing agents may be used singly or in combination of two or more.

In the present invention, it is particularly preferred to use a pigment derivative in combination with a polymer dispersant. Further, the pigment dispersant may be used together with the terminal-modified polymer having a fixed portion on the surface of the pigment, a graft polymer, or a block-type polymer, together with an alkali-soluble resin. Examples of the alkali-soluble resin include a (meth)acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and a carboxylic acid in a side chain. An acidic cellulose derivative, particularly preferably a (meth)acrylic copolymer. In addition, the N-substituted maleimide monomer copolymer described in Japanese Laid-Open Patent Publication No. Hei 10-300922, and the ether dimer copolymer described in JP-A-2004-300204, An alkali-soluble resin containing a polymerizable group described in Japanese Laid-Open Patent Publication No. Hei 7-319161.

Further, it is also preferred to use a dispersant having the following structure.

(In the above, a is 2.0, b is 4.0, acid value is 10 mgKOH/g, and Mw is 20000. In addition, a and b respectively represent the number of partial structures represented in parentheses, satisfying a+b=6)

In the present invention, the (C) dispersant is particularly preferably a component obtained by reacting the hydroxyl group of a vinyl polymer having a hydroxyl group at a single terminal with a tricarboxylic anhydride or a tetracarboxylic dianhydride. Powder. Hereinafter, a dispersant obtained by reacting the hydroxyl group of a vinyl polymer having a hydroxyl group at a single terminal with a tricarboxylic anhydride or a tetracarboxylic dianhydride will be described. By using such a compound, the adsorption force between the (B) and the heterocyclic ring of the pigment derivative is improved, and the effects of the present invention are more effectively exhibited.

- a vinyl polymer having a hydroxyl group at one end -

The vinyl polymer having a hydroxyl group at a single terminal is preferably a polymer represented by the following formula (1). The polymer represented by the formula (1) is a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer.

General formula (1)

(In the formula (1), Y ² represents a polymerization stop group of a vinyl polymer, Z ² represents -OH or R ²⁸ (OH) ₂ , and R ²⁸ represents a trivalent hydrocarbon group having 1 to 18 carbon atoms, and R ²¹ and R ²² denotes a hydrogen atom or a methyl group, respectively, and any of R ²³ and R ²⁴ represents a hydrogen atom, and the other represents an aromatic group or -C(=O)-X ⁶ -R ²⁵ (wherein, X ⁶ represents -O- or -N(R ²⁶ )-, and R ²⁵ and R ²⁶ each represent a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms which may have an aromatic group as a substituent, and X ⁴ represents a single bond. -OR ²⁷ - or SR ²⁷ -, R ²⁷ represents a linear or branched alkyl group having 1 to 18 carbon atoms, and n represents an integer of 2 to 50)

Y ² represents a polymerization stop group of a vinyl polymer, and is any known polymerization stop group introduced when a normal ethylenically unsaturated monomer is polymerized by a usual method. For example, it may be a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Even if Y ² has any of these chemical structures, the dispersing agent of the present invention can exert its effects without being affected by the polymerization stopping group Y ² . The polymerization stop group may, for example, be a carboxylic acid residue or an alcohol residue, and is preferably a carboxylic acid residue.

Z ² represents -OH or R ²⁸ (OH) ₂ , preferably -OH.

R ²⁸ represents a trivalent hydrocarbon group having 1 to 18 carbon atoms. R ^{28 is} preferably a trivalent hydrocarbon group having 1 to 18 carbon atoms, more preferably a trivalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a trivalent hydrocarbon group having 1 to 6 carbon atoms. The trivalent hydrocarbon group may be an alkane formed by removing three hydrogen atoms from a saturated hydrocarbon molecule having 1 to 18 carbon atoms such as methane, ethane, propane, 2-methylpropane, butane, cycloheptane and cyclohexane. a group formed by removing three hydrogen atoms from an aromatic hydrocarbon molecule having 6 to 18 carbon atoms such as benzene, naphthalene, anthracene, tetracene, biphenyl, anthracene, anthracene, pyrene, and pyridine. Preferably, it is a group formed by removing three hydrogen atoms from benzene.

R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and preferably a hydrogen atom.

Any one of R ²³ and R ²⁴ represents a hydrogen atom, and the other represents an aromatic group or -C(=O)-X ⁶ -R ²⁵ (wherein, X ⁶ represents -O- or -N(R ²⁶ )-). The aromatic group is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 14 carbon atoms, and more preferably an aromatic group having 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, a fluorenyl group and the like

X ⁶ represents -O- or -N(R ²⁶ )-, and R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having a linear or branched carbon number of 1 to 18 and having an aromatic group as a substituent. The linear or branched alkyl group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof 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, a n-hexyl group, and an n-octyl group. The aromatic group which is a substituent of the alkyl group is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 14 carbon atoms, and more preferably an aromatic having 6 to 10 carbon atoms. Family base. Specific examples thereof include a phenyl group, a naphthyl group, a fluorenyl group and the like

X ⁴ represents a single bond, -OR ²⁷ - or SR ²⁷ -, preferably SR ²⁷ -.

R ²⁷ represents a linear or branched alkyl group having 1 to 18 carbon atoms. The alkylene group having 1 to 18 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. Specific examples thereof include a methylene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group.

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

The portion of the repeating unit of the polymer represented by the general formula (1), that is, {-[C(R ²¹ )(R ²³ )-C(R ²² )(R ²⁴ )] _n -} may be the same as each other The (homopolymer) may also be a (copolymer) containing different ones. A preferred embodiment of the polymer represented by the above formula (1) is a case where either one of R ²¹ and R ²² is a hydrogen atom, the other is a hydrogen atom or a methyl group, and any of R ²³ and R ²⁴ is a hydrogen atom and the other is -C(=O)-OR ²⁹ (R ²⁹ is a linear or branched alkyl group having 1 to 8 carbon atoms and may have an aromatic group as a substituent), -X ⁴ - Z ² is -S-CH ₂ CH ₂ -OH or -S-CH ₂ CH(OH)CH ₂ -OH.

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

- Tricarboxylic anhydride or tetracarboxylic dianhydride -

The tricarboxylic acid anhydride may first be an aliphatic tricarboxylic anhydride or an aromatic tricarboxylic anhydride.

Examples of the aliphatic tricarboxylic anhydride include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, and cis-propylene-1,2,3-tricarboxylic acid. -1,2-anhydride, 1,3,4-cyclopentanetricarboxylic anhydride, and the like.

Examples of the aromatic tricarboxylic anhydride include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride), etc.), and naphthalene tricarboxylic anhydride (1). , 2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4 '-benzophenone tricarboxylic anhydride, 3,4,4'-diphenyl ether tricarboxylic anhydride, 3,4,4'-biphenyl tricarboxylic anhydride, 2,3,2'-biphenyl tricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, 3,4,4'-biphenylfluorene tricarboxylic anhydride, and the like.

In the case of using a tricarboxylic anhydride, the aromatic tricarboxylic anhydride is preferred.

Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and polycyclic tetracarboxylic dianhydride.

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-tricarboxycyclopentyl acetic acid dianhydride , 2,3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6- Tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranmethylidene)-3-methyl-3- Cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol trimellitic anhydride, propylene glycol trimellitic anhydride, butanediol trimellitic anhydride, and 3, 3'. , 4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl fluorene Carboxylic dianhydride, 2,2',3,3'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3' , 4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Thioether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Propane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(o-benzene) Dicarboxylic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylphthalic acid) dianhydride, double (three Phenylphthalic acid)-4,4'-diphenyl ether Dihydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)ruthenic anhydride, 9,9-double [4-(3,4-Dicarboxyphenoxy)phenyl]phthalic anhydride or the like.

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

In the case of using a tetracarboxylic dianhydride, the aromatic tetracarboxylic acid is preferred. Acid dianhydride.

The tricarboxylic anhydride or tetracarboxylic dianhydride used in the present invention is not limited to the above-exemplified compounds, and any structure may be employed. These compounds may be used singly or in combination. From the viewpoint of the low viscosity of the pigment dispersion or various inks, an aromatic tricarboxylic anhydride or an aromatic tetracarboxylic dianhydride can be preferably used in the present invention. Further preferred are pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)sebacic anhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, ethylene glycol trimellitic anhydride, trimellitic anhydride.

Next, a step of reacting the hydroxyl group of the vinyl polymer having a hydroxyl group at a single terminal with an acid anhydride group of an aromatic tricarboxylic anhydride will be described.

When the number of moles of the hydroxyl group of the vinyl polymer having a hydroxyl group at a single terminal is set to <H>, and the number of moles of the carboxylic anhydride group of the aromatic tricarboxylic anhydride is set to <N>, the reaction ratio is preferably 0.3≦<H>/<N>≦3, and further preferably 0.5≦<H>/<N>≦2.

A catalyst may also be used in the reaction of the ethylene-based polymer having a hydroxyl group at the single terminal and the aromatic tricarboxylic anhydride.

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

The reaction of the hydroxyl group of the ethylene-based polymer having a hydroxyl group at a single terminal with the acid anhydride group of the aromatic tricarboxylic acid anhydride can be carried out without a solvent, and a suitable dehydrated organic solvent can also be used. The solvent used in the reaction can be distilled, etc. after the reaction is completed. Used to remove, or used directly as part of a dispersant product. The solvent to be used is not particularly limited, and ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether B can be used. Acid ester, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate Ester and the like. These solvents may be used in combination of two or more kinds.

The reaction temperature of the hydroxyl group of the ethylene-based polymer having a hydroxyl group at a single terminal and the acid anhydride group of the aromatic tricarboxylic acid anhydride is preferably in the range of from 50 ° C to 180 ° C, more preferably from 60 ° C to 160 ° C. . When the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 180 ° C, the reaction may be carried out, and the ring-opened acid anhydride may again form a cyclic anhydride, and the reaction may not be completed.

<(D) Photopolymerization initiator>

The composition of the present invention contains a photopolymerization initiator in terms of further improving the sensitivity.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound described later, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred to have a sensitivity to ultraviolet light to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-excited sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.

Further, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm, more preferably 330 nm to 500 nm.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, etc.), a decylphosphine oxide such as acyl phosphine oxide, or a hexaaryl group. An anthracene compound such as a biimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone.

Further, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzoin dimethyl ketal compound, an α-hydroxyketone compound, an α-amino ketone compound, and a mercaptophosphine. Compound, phosphine oxide compound, metallocene compound, hydrazine compound, triaryl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene- A compound of the group consisting of an iron complex and a salt thereof, a halogenated methyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

Further preferred are trihalomethyltriazine compounds, α-amino ketone compounds, mercaptophosphine compounds, phosphine oxide compounds, ruthenium compounds, triarylimidazole dimers, triarylimidazole compounds, benzimidazole compounds, ruthenium compounds a benzophenone compound or an acetophenone compound, particularly preferably selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, a hydrazine compound, a triaryl imidazole compound, a benzophenone compound, and a triaryl imidazole. At least one compound of the group consisting of a compound and a benzimidazole compound. Further, the triarylimidazole compound may also be a mixture with benzimidazole.

Specifically, the trihalomethyltriazine compound can be exemplified by the following compounds. Further, Ph is a phenyl group.

[39]

The triaryl imidazole compound and the benzimidazole compound can be exemplified by the following compounds.

A commercially available product can also be used as the trihalomethyltriazine compound, and 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 producing a color filter provided in a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape. Therefore, it is important that the hardenability is in the unexposed portion. Development was carried out without residue. From this point of view, the photopolymerization initiator is particularly preferably a ruthenium compound. In particular, when a fine pattern is formed in a solid-state image sensor, stepwise exposure is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to be low. Therefore, if these aspects are taken into consideration, it is particularly good to form a solid In the case of a fine pattern like a bulk image sensor, a ruthenium compound is used as the (D) photopolymerization initiator.

Examples of the halogenated hydrocarbon derivative having a triazine skeleton include a compound described in "Bull. Chem. Soc. Japan" (42, 2924 (1969)), and a British patent. The compound described in the specification of Japanese Patent No. 1388492, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the "organic chemistry journal of FC Schaefer (FC Schaefer), etc. The compound described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in Japanese Laid-Open Patent Publication No. Hei 5-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

The compound described in the specification of the U.S. Patent No. 4,212,976 is exemplified by a compound having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-three Chloromethyl-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-tri Chloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4 -oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1 , 3,4-oxadiazole, etc.).

Further, examples of the photopolymerization initiator other than the above may be exemplified by an acridine derivative (example) Such as 9-phenyl acridine, 1,7-bis (9,9'-acridinyl) heptane, etc., N-phenylglycine, etc., polyhalogen compounds (such as carbon tetrabromide, Phenyl tribromomethyl hydrazine, phenyl trichloromethyl ketone, etc.), coumarins (eg 3-(2-benzofuranyloxy)-7-diethylamino coumarin, 3-( 2-benzopyryl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-diethylaminocoumarin, 3-(2-methoxybenzoate Mercapto)-7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl)-7-diethylamino coumarin, 3,3'-carbonyl bis ( 5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzylidene-7-methoxycoumarin , 3-(2-indolyl)-7-diethylamino coumarin, 3-(4-diethylaminocinnamino)-7-diethylamino coumarin, 7- Methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, In addition, Japanese Patent Laid-Open No. Hei 5-19475, Japanese Patent Laid-Open No. Hei 7-271028, Japanese Patent Laid-Open Publication No. 2002-363206, and Japanese Patent Laid-Open No. 2002-363207 Japanese Patent Publication No. 2002-363208, coumarin compounds and the like described in JP-A-2002-363209, etc., phosphinylphosphines (for example, bis(2,4,6-trimethylbenzene) Mercapto)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (eg 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., Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent No. Sho 57 The compound described in the specification of the Japanese Patent Publication No. Hei. No. Hei.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, and 4-methoxybenzophenone. 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid Or a tetramethyl ester thereof, 4,4'-bis(dialkylamino)benzophenone (for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'- Bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone) , 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethyl Acetophenone acetophenone, benzoin, anthracene, 2-tert-butylhydrazine, 2-methylindole, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-thiazepine Ketone, 2,4-diethylthianone, anthrone, 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol Polymer Aromatic and benzoin ethers (eg, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzoin dimethyl ketal), acridone, chloroacridone, N-methyl Acridone, N-butylacridone, N-butyl-chloroacridone, and the like.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969 and a cerium oxide-based phosphine-based initiator described in Japanese Patent No. 4,258,899 can be used.

The hydroxyacetophenone-based initiator can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, Yanjiagu (IRGACURE)-2959, IRGACURE-127 (trade name: all manufactured by BASF). Amino acetophenone-based initiators can be used: IRGACURE-907, IRGACURE-369 and IRGACURE-379, IRGACURE, which are commercially available products. - OXE379 (trade name: all manufactured by BASF). The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched to a long-wavelength light source such as 365 nm or 405 nm. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF) can be used as a commercial product.

More preferably, the photopolymerization initiator is a ruthenium compound. For the specific example of the ruthenium compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used.

As the ruthenium compound such as an anthracene derivative which can be preferably used as the photopolymerization initiator of the present invention, for example, 3-benzylideneoxyiminobutan-2-one and 3-ethyloxyimide can be cited. Butyral-2-one, 3-propoxy methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino group- 1-phenylpropan-1-one, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2- Ketone and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

In addition, the bismuth compound can be listed as "Journal of the Chemical Society (J.C.S.) Perkin II (1979) Pp.1653-1660, "Journal of the Chemical Society (JCS) Perkin II (1979) pp. 156-162, "Journal of Photopolymer Science and Technology" Photopolymer Science and Technology) (1995) pp. 202-232, Japanese Patent Laid-Open Publication No. 2000-66385, Japanese Patent Laid-Open Publication No. 2000-80068, Japanese Patent Publication No. 2004-534797, A compound or the like described in each of the publications of JP-A-2006-342166.

Commercially available products are also preferably used in IRGACURE-OXE01 (BASF), IRGACURE-OXE02 (BASF), TR-PBG-304 (Changzhou) Made by Powerful Electronic New Materials Co., Ltd.).

In addition, the following compounds may be used as the ruthenium compound other than the above-mentioned compound: the compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is bonded to the N-position of the carbazole, and the impurity introduced into the benzophenone moiety. The compound described in the U.S. Patent No. 7,626,957, the compound, the compound described in Japanese Patent Laid-Open No. 2010-15025, and the U.S. Patent Publication No. 2009-292039, the entire disclosure of which is incorporated herein by reference. Japanese Patent No. 7556910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, and a Japanese patent having a maximum absorption at 405 nm and having a good sensitivity to a g-ray source. The compound or the like described in JP-A-2009-221114.

It is preferable to further preferably use Japanese Patent Laid-Open No. 2007-231000 The cyclic anthraquinone compound described in Japanese Laid-Open Patent Publication No. 2007-322744. In the case of the cyclic ruthenium compound, in particular, it is described in Japanese Patent Laid-Open No. 2010-32985, and Japanese Patent Laid-Open Publication No. 2010-185072. A cyclic guanidine compound in which an azole pigment is condensed.

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of a ruthenium compound, also regenerates an active radical by polymerizing an inactive radical, thereby achieving high sensitivity and being comparable. Good to use.

The ruthenium compound having a specific substituent disclosed in Japanese Laid-Open Patent Publication No. 2007-269779, or the ruthenium compound having a thioaryl group as shown in JP-A-2009-191061.

Specifically, the ruthenium compound as a photopolymerization initiator is preferably a compound represented by the following formula (OX-1). Further, the ruthenium compound in which the NO bond of ruthenium is (E) may be a ruthenium compound in which the NO bond of ruthenium is (Z), or the NO bond of ruthenium may be (E) and (Z) a mixture of bodies.

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

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

The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. In addition, the groups may have more than one substituent. Further, the substituent may be further substituted with other substituents.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group, an aryl group and the like.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include 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, and an isopropyl group. Base, isobutyl, second butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzamidine methyl, 1-naphthalene Methylmercaptomethyl, 2-naphthylmethylmethyl, 4-methylamine benzenesulfonylbenzhydrylmethyl, 4-phenylamine sulfanil benzamidine methyl, 4-dimethyl Aminobenzyl benzhydryl methyl, 4-cyanobenzhydrylmethyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl, 3- Trifluoromethylbenzimidylmethyl and 3-nitrobenzimidylmethyl.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 9-phenanthryl group, and a 1-fluorenyl group. 5-nphthacenyl, 1-indenyl, 2-indenyl, 9-indenyl, terphenyl, tetraphenyl, o-tolyl, m-tolyl, p-tolyl, xylene Base, ortho-alkenyl, m-cumenyl and p-cumenyl, 2,4,6-trityl, pentalenyl, binaphthalenyl, trinaphthyl , tetranaphthyl, heptalenyl, biphenylenyl, indacenyl, fluoranthenyl, fluorenyl (acenaphthylenyl), aceanthrylenyl, phenalenyl, fluorenyl, fluorenyl, hydrazino, triple fluorenyl, tetradecyl, anthraquinolyl, phenanthryl, Benzo[9,10]triphenylenyl, fluorenyl, Chrysenyl, condensed tetraphenyl, pleiadenyl, picenyl, perylenyl, pentaphenyl, pentacenyl, tetraphenylenyl , hexaphenyl, hexaphenyl, rubicenyl, coronenyl, trinaphthylenyl, heptaphenyl, hexaphenyl, pyranthrenyl and ovalenyl ).

The fluorenyl group is preferably a fluorenyl group having 2 to 20 carbon atoms, and specific examples thereof include an ethyl group, a propyl group, a butyl group, a trifluoroethyl group, a pentamidine group, a benzamidine group, a 1-naphthylmethyl group, 2-naphthylmethyl, 4-methylamine phenylsulfonylbenzyl, 4-phenylamine phenylsulfonylbenzyl, 4-dimethylaminobenzimidyl, 4-diethyl Aminobenzylidene, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzhydryl, 3-chlorobenzhydrazide , 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzylidene and 4- Methoxybenzhydryl.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, and an octyloxy group. A carbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethoxycarbonyl group.

Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylamine benzenesulfonylphenoxycarbonyl group, and a 4-phenylamine benzenesulfonylphenoxy group. Carbocarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxybenzene Oxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxycarbonyl 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl and 4-methoxyphenoxycarbonyl.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specific examples thereof include: thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, pyranyl, isobenzofuranyl, benzopyrazine Chromenyl, Xanthenyl, phenoxathiinyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridazinyl, isoindole , 3H-indenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quinolizinyl, isoquinolinyl, quinolyl, phthalazinyl, naphthyridinyl, Quinoxalinyl, quinazolinyl, Cinnolinyl, pteridinyl, 4aH-carbazolyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl , morpholinyl, phenazinyl, phenarsazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenoxazine Basis Isochromanyl, benzochromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, piperazinyl, porphyrin A base, an isoindolyl group, a quinuclidinyl group, a morpholinyl group, and a thioxantrill.

Specific examples of the alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, a octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and a trifluoromethylthio group. Carbonyl.

Specific examples of the arylthiocarbonyl group include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylaminobenzenesulfonylphenylthiocarbonyl, 4-phenylaminebenzenesulfophenylthiocarbonyl, 4- Dimethylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthiocarbonyl, 2 -butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4-fluorobenzene Thiocarbonyl, 4-cyanophenylthiocarbonyl and 4-methoxyphenylthiocarbonyl.

In the formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. In addition, the groups may have more than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among them, the structure shown below is particularly preferable.

In the following structures, Y, X and n are the same as Y, X and n in the following general formula (OX-2), and preferred examples are also the same.

[化42]

In the formula (OX-1), the divalent organic group represented by A may, for example, be an alkylene group having a carbon number of 1 to 12, a cycloalkylene group or an alkynylene group. In addition, the groups may have more than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among them, in terms of improving sensitivity and suppressing coloring caused by heating over time, A in the formula (OX-1) is preferably an unsubstituted alkylene group or an alkyl group (e.g., methyl group, ethyl group). , a tert-butyl, dodecyl) substituted alkylene group, an alkyl group substituted by an alkenyl group (e.g., a vinyl group, an allyl group), an aryl group (e.g., phenyl, p-tolyl, xylyl) , cumenyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkylene.

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. The substituent may be exemplified by the same group as the substituent introduced on the substituted aryl group exemplified above as a specific example of the aryl group which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferred in terms of improving sensitivity and suppressing coloration caused by heating over time.

In the formula (OX-1), in terms of sensitivity, the structure of "SAr" formed by Ar in the formula (OX-1) and S adjacent thereto is preferably the structure shown below. Further, Me represents a methyl group, and Et represents an ethyl group.

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

[化44]

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

In the general formula (OX-2), the monovalent substituent represented by X may, for example, be an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a decyl group, an alkoxycarbonyl group, an amine group or a hetero group. Ring group, halogen atom. In addition, the groups may have more than one substituent. The substituents described above can be exemplified as the substituents described above. Further, the substituents described above may be further substituted with other substituents.

Among these, X in the formula (OX-2) is preferably an alkyl group in terms of improving solvent solubility and absorption efficiency in a long wavelength range.

Further, n in the formula (OX-2) represents an integer of 0 to 5, preferably an integer of 0 to 2.

In the general formula (OX-2), the divalent organic group represented by Y may be exemplified by the structures shown below. Further, in the group shown below, "*" represents a bonding position of a carbon atom adjacent to Y in the formula (OX-2).

[化45]

Among them, from the viewpoint of high sensitivity, the structure shown below is preferable.

Further, the ruthenium compound is preferably a compound represented by the following formula (OX-3) or (OX-4).

[化47]

In the formula (OX-3) or the formula (OX-4), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0-5.

R, X, A, Ar and n in the formula (OX-3) or (OX-4) are the same as R, X, A, Ar and n in the formula (OX-2), respectively The meaning is the same and the preferred examples are the same.

Hereinafter, specific examples (C-4) to specific examples (C-13) of the ruthenium compound which can be preferably used are shown below, but the present invention is not limited to these specific examples.

[48]

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

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000.

The molar absorption coefficient of the compound can be determined by a known method, specifically For example, it is preferable to use an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian Co., Ltd.), and use an ethyl acetate solvent at 0.01 g/L. The concentration was measured.

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

The content of the (D) photopolymerization initiator in the composition of the present invention is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass based on the total solid content of the composition. Hereinafter, it is preferably 1% by mass or more and 3% by mass or less. Better sensitivity and pattern formation can be obtained within this range.

<<(E) Polymeric Compound>>

The composition of the present invention contains (E) a polymerizable compound. In the present invention, a known polymerizable compound which can be crosslinked by a radical, an acid or a heat can be used, and examples thereof include an ethylenically unsaturated bond and a cyclic ether (epoxy or oxetane). A polymerizable compound such as a methylol group. From the viewpoint of sensitivity, the (E) polymerizable compound is preferably selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Among them, a polyfunctional polymerizable compound having four or more functional groups is preferable, and a polyfunctional polymerizable compound having five or more functional groups is more preferable.

Such a compound group is widely known in the industrial field, and these compounds can be used without particular limitation in the present invention. These compounds may be, for example, any of the following chemical forms: a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture thereof, and the like. The polymerizable compounds of the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof. The guanamines and the polymers thereof are preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and guanamines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and the like. Things. Further, it is also preferred to use the following reactants: an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition of a monofunctional or polyfunctional isocyanate or epoxy group. a reactant, or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, or the like. Further, the following reactants are also preferred: an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. The reactants further include a substituted carboxylic acid ester of a detachable substituent such as a halogen group or a tosyloxy group, or a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a compound group of a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead of the unsaturated carboxylic acid.

As the specific compound, the compound described in Paragraph No. [0095] to Paragraph No. [0108] of JP-A-2009-288705 is preferably used in the present invention.

Further, the polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one vinyl group capable of undergoing addition polymerization and having a boiling point of 100 ° C or higher at normal pressure. Examples thereof include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Energy acrylate or methacrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol three (Meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylol Propane tris(propylene oxypropyl)ether, tris(propylene decyloxyethyl)isocyanate, addition of ethylene oxide or a ring to a polyfunctional alcohol such as glycerol or trimethylolethane The oxypropane is obtained by a (meth) acrylate, and is described in Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. SHO-50-63034, and JP-A-53-37193 ( The polyester acrylates described in JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490, Polyfunctional propylene such as epoxy acrylate such as a reaction product of an epoxy resin and (meth)acrylic acid An acid ester or methacrylate and a mixture of these.

Further, a polyfunctional (meth) acrylate such as a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate and a polyfunctional carboxy group may be mentioned. Obtained by acid reaction.

In addition, other preferred polymerizable compounds may have an anthracene ring and have an anthracene ring as described in JP-A-2010-160418, JP-A-2010-129825, and Japanese Patent No. 4,364,216. A compound having two or more functional ethylenically unsaturated groups, a cardo resin.

Further, a compound having a boiling point of 100 ° C or more under normal pressure and having at least one ethylenically unsaturated group capable of undergoing addition polymerization is also preferably a Japanese patent. The compound described in Paragraph No. [0254] to Paragraph No. [0257] of JP-A-2008-292970.

In addition to the above compounds, a radical polymerizable monomer represented by the following formula (MO-1) to formula (MO-5) can be preferably used. Further, in the case where T is an oxygen-extended alkyl group, the terminal on the carbon atom side is bonded to R.

[化50]

In the above formula (MO-1) to formula (MO-5), n is 0 to 14 and m is 1 to 8. R and T which are present in a plurality of molecules may be the same or different.

In each of the polymerizable compounds represented by the above formula (MO-1) to formula (MO-5), at least one of a plurality of Rs represents -OC(=O)CH=CH ₂ or -OC ( =O) C(CH ₃ )= group represented by CH ₂ .

Specific examples of the polymerizable compound represented by the above formula (MO-1) to (MO-5) can also be described in paragraph number 0248 to paragraph number 0251 of JP-A-2007-269779. The compounds are preferably used in the present invention.

In addition, the following compounds can also be used as the above-mentioned polyfunctional compound as described in the general formula (1) and the general formula (2) in the Japanese Patent Publication No. Hei 10-62986. A compound obtained by adding (meth)acrylic acid to ethylene after adding ethylene oxide or propylene oxide.

Among them, the polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) propylene The thiol group is separated from the structure of the ethylene glycol residue and the propylene glycol residue. These types of oligomers can also be used. The aspect of the preferred polymerizable compound is shown below.

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

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has a non-aromatic carboxylic anhydride reacting with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The polyfunctional monomer is particularly preferably one in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Commercially available products include M-510 and M-520 which are polybasic acid-modified acrylic oligomers manufactured by East Asia Synthetic Co., Ltd., for example.

These monomers may be used singly, but it is difficult to use a single compound in terms of production, and it is also possible to use two or more kinds in combination. In addition, as needed A polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group are used as a monomer.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is too low, development and dissolution characteristics are lowered, and if it is too high, production or handling becomes difficult, photopolymerization performance is lowered, and hardenability such as surface smoothness of pixels is deteriorated. Therefore, in the case where two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred that the acid group of the entire polyfunctional monomer is in the The way the range is adjusted.

Further, a polyfunctional monomer having a caprolactone structure is also preferred as a polymerizable monomer.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate, and ε- Caprolactone modified polyfunctional (meth) acrylate by trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, two Polyols such as pentaerythritol, tripentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (Z-1) is preferred.

[化51]

In the general formula (Z-1), all of the six R groups are groups represented by the following formula (Z-2), or one to five of the six R groups are represented by the following formula (Z-2). The group represented by the group and the rest are groups represented by the following formula (Z-3).

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

In the 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, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (the formula (Z-1) m = 1 in the formula (Z-3), the number of groups represented by the formula (Z-2) = 2, the compound in which all of R ¹ are a hydrogen atom), DPCA-30 (the formula (Z-) 1) where m = 1 in the formula (Z-3), the number of groups represented by the formula (Z-2) = 3, and the compound in which all R ¹ are a hydrogen atom), DPCA-60 (the formula (Z) -1)~ m = 1 in the formula (Z-3), the number of groups represented by the formula (Z-2) = 6, a compound in which all R ¹ are a hydrogen atom), DPCA-120 (the formula ( Z-1)~ wherein m=2 in the formula (Z-3), the number of groups represented by the formula (Z-2) = 6, and all compounds in which R ¹ is a hydrogen atom).

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

Further, the polymerizable monomer which can be used in the present invention is preferably at least one selected from the group consisting of compounds represented by the following formula (Z-4) or (Z-5).

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

In the above formula (Z-4), the total of the acryloyl group and the methacryl fluorenyl group is 3 or 4, and m each independently represents an integer of 0 to 10, and the total value of each m is 0 to 40. The integer. In the case where the total value of each of m is 0, any one of X is a carboxyl group.

In the above formula (Z-5), the total of the acryloyl group and the methacryl fluorenyl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the total value of each n is 0 to 60. The integer. However, when the total value of each n is 0, any one of X is a carboxyl group.

In the above formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

Further, the total value 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 above formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

Further, the total value 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.

Further, -((CH ₂ )yCH ₂ O)- or -((CH ₂ )yCH(CH ₃ )O)- in the formula (Z-4) or the formula (Z-5) is preferably an oxygen atom. The end of the side is bonded to the form of X.

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. Particularly preferred is a form in which all six of X in the formula (Z-5) are an acrylonitrile group.

In addition, the total content of the compound represented by the formula (Z-4) or the 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 formula (Z-4) or the formula (Z-5) can be synthesized by the following steps as a previously known step: ethylene oxide or propylene oxide by a ring-opening addition reaction a step of bonding a ring-opening skeleton to pentaerythritol or dipentaerythritol; and a step of introducing, for example, (meth)acrylofluorene chloride with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group. Each step is a well-known step, and a compound represented by the formula (i) or the formula (ii) can be easily synthesized by those skilled in the art.

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

Specific examples thereof include the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to exemplified compounds (f)"). Among them, preferred examples are compounds (a) and exemplified. Compound (b), exemplified compound (e), and exemplified compound (f).

[化55]

[化56]

Commercial products of the polymerizable compound represented by the formula (Z-4) and the formula (Z-5) include, for example, a tetrafunctional acrylic acid having four ethylene oxide chains manufactured by Sartomer Co., Ltd. Ester SR-494, a hexafunctional acrylate DPCA-60 having six pentyloxy chains, three trifunctional acrylates TPA-330 having an extended isobutoxy chain, and the like, manufactured by Nippon Kayaku Co., Ltd.

In addition, the polymerizable compound is also preferably a Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Laid-Open No. 2-16765 Acetyl amides as described in the publication, Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, and Japanese Patent Publication No. SHO 62-39417 A urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 62-39418. In addition, the intramolecular structure having an amine structure or a thioether structure as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As the polymerizable compound, an addition polymerizable compound can obtain a curable composition having a very excellent photospeed.

Commercial products of the polymerizable compound include urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), and "UA-7200" (new Made by Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha), Trihydroxyl Propane triacrylate (commercially available as A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.).

Regarding a cyclic ether (epoxy or oxetane), for example, as an epoxy group, the bisphenol A type epoxy resin is JER-827, JER-828, JER-834, JER-1001, JER-1002. , JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (above is made by Japan Epoxy Resin Co., Ltd.), Epiclon 860, Epiclon 1050, Ai Epiclon 1051, Epiclon 1055 (above is manufactured by Di Aisheng (DIC) Co., Ltd.); bisphenol F epoxy resin is JER-806, JER-807, JER-4004, JER -4005, JER-4007, JER-4010 (above is made by Japan Epoxy Resin Co., Ltd.), Epiclon 830, EPICLON 835 (above DIC) ), LCE-21, RE-602S (above is Nippon Chemical Co., Ltd.) Manufacturing), etc.; phenol novolak type epoxy resin is JER-152, JER-154, JER-157S70, JER-157S65 (above is made by Japan Epoxy Resin Co., Ltd.), Apic clone (EPICLON) N-740, EPICLON N-770, EPICLON N-775 (above), etc.; cresol novolac epoxy resin is Epiclon N -660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N -690, Epiclon (EPICLON) N-695 (above is manufactured by Di Aisheng (DIC) Co., Ltd.), EOCN-1020 (above is manufactured by Nippon Kayaku Co., Ltd.); aliphatic epoxy resin can be listed as: ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above ADEKA) Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE-3150 (2,2-bis(hydroxymethyl)- 1,2-epoxy-4-(2-oxopropyl)cyclohexane adduct of 1-butanol), Apollo (EPOLEAD) PB 3600, EPOLEAD PB 4700 (above produced by Daicel Chemical Industry Co., Ltd.), Denacol EX-211L, Denacol EX- 212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L (The above is a long 濑Nagase Chemtex (manufactured by Nagase Chemtex), ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, Ai ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above ADEKA), NC-2000, NC-3000, NC-7300, XD -1000, EPPN-501, EPPN-502 (above is manufactured by ADEKA), JER-1031S (made by Nippon Epoxy Co., Ltd.), and the like. Such a polymerizable compound is suitable for the case where a pattern is formed by dry etching.

The details of the use of the polymerizable compound, such as the structure, the use alone or in combination, and the amount of addition, can be arbitrarily set depending on the final performance design of the colored photosensitive resin composition. For example, from the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably a difunctional or higher. In addition, from the viewpoint of improving the strength of the cured film formed of the colored photosensitive resin composition, it is preferably a trifunctional or higher functional group, and further, a combination of different functional groups and different polymerizable groups (for example, acrylate, A method of adjusting both sensitivity and strength by a methacrylate, a styrene compound, or a vinyl ether compound is also effective. Further, it is preferable to use a polymerizable compound having a trifunctional or higher functional group and a different ethylene oxide chain length in order to adjust the developability of the colored photosensitive resin composition, and to obtain excellent pattern forming ability.

In addition, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, etc.) contained in the coloring photosensitive resin composition, and the selection of a polymerizable compound. The use method is also an important factor. For example, it is sometimes possible to improve the compatibility by using a low-purity compound or a combination of two or more. In addition, from the viewpoint of improving the adhesion to a hard surface such as a support, it is sometimes possible to select a special The structure.

The content of the (F) polymerizable compound in the composition of the present invention is preferably from 3% by mass to 25% by mass, and more preferably from 5% by mass to 20% by mass based on the total solid content of the colored photosensitive resin composition. , particularly preferably from 7 mass% to 15 mass%.

<<Other ingredients>>

In addition to the above-described respective components, the composition of the present invention may further contain (G) a resin having a polymerizable double bond in a side chain, an organic solvent, a crosslinking agent, etc., insofar as the effects of the present invention are not impaired. ingredient.

- (G) a resin having a polymerizable double bond in a side chain -

In the present invention, a resin having a polymerizable double bond in the side chain (G) (hereinafter also referred to as "(G) resin") may be further contained. The composition of the present invention can be more effectively cured by further containing a resin having a polymerizable double bond in the (G) side chain.

(G) The resin having a polymerizable double bond in the side chain is not particularly limited as long as it has a polymerizable double bond in the side chain, and it is preferred to have a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond. A compound (b) and a resin obtained by reacting a polymerizable monomer (p) having two to six hydroxyl groups with a copolymer (a) of another polymerizable monomer (q).

The polymerizable monomer (p) having two to six hydroxyl groups in the resin having a polymerizable double bond in the side chain of (G) is a compound having two or more and six or less hydroxyl groups and an ethylenically unsaturated double bond. For example, a monomer represented by the following formula (1) can be used.

General formula (1)

(wherein R ¹ and R ⁴ each independently represent a hydrogen atom, a 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 number of 1 to 4; An alkyl group or a single bond, and n represents an integer of 2 or more and 6 or less)

The monomer represented by the above formula (1) may, for example, be a monoester of a polyhydric alcohol having an ethylenically unsaturated double bond, and is preferably a mono(meth)acrylate.

The other polymerizable monomer (q) is a polymerizable monomer copolymerizable with the polymerizable monomer (p) having 2 to 6 hydroxyl groups, and examples thereof include (meth)acrylic acid and (meth)acrylic acid. Ester, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Tributyl ester, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethyl (meth) acrylate a (meth) acrylate such as hexyl ester, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate or tetrahydrofurfuryl (meth)acrylate; N-vinylpyrrolidone; Styrene and its derivatives, styrenes such as α-methylstyrene; (meth) acrylamide, hydroxymethyl (meth) acrylamide, alkoxy hydroxymethyl (meth) acrylamide And acrylamide such as diacetone (meth) acrylamide; other vinyl compounds such as (meth)acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate; and polymethyl methacrylate Monomer, poly Giant monomers such as styrene giant monomers. These monomers may be used alone or in combination of two or more.

Further, the copolymerization of the polymerizable monomer (p) having 2 to 6 hydroxyl groups and the other polymerizable monomer (q) is preferably 5% by mass to 95% by mass: 95% by mass to 5% by mass, more preferably It is 30% by mass to 70% by mass: 70% by mass to 30% by mass. When the copolymerization ratio of the polymerizable monomer (p) is less than 5% by mass, the number of ethylenically unsaturated double bonds which can be introduced is small, and the value of the double bond equivalent (the double bond equivalent defined by the following formula) becomes large. , can not get full sensitivity. When the copolymerization ratio of the polymerizable monomer (p) exceeds 95% by mass, a large amount of ethylenically unsaturated double bonds can be introduced, but the ratio of the polymerizable monomer (q) becomes low, so that it is difficult to maintain dispersion stability. Physical properties such as solubility and chemical resistance.

The production of the copolymer (a) having a polymerizable monomer (p) having 2 to 6 hydroxyl groups and another polymerizable monomer (q) can be produced by a known method, and for example, refer to Japanese Patent Laid-Open No. 2005-156930. The description of paragraph 0013 of the Gazette is incorporated into the present specification.

(G) A resin having a polymerizable double bond in a side chain is obtained by reacting a compound (b) having a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond with the copolymer (a). Examples of the functional group capable of reacting with a hydroxyl group of the compound (b) having a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond include an isocyanate group and a carboxyl group, and particularly preferably in terms of reactivity. Isocyanate group.

Specific examples of the compound having an isocyanate group and an ethylenically unsaturated double bond include 2-propenylethyl isocyanate and 2-methylpropenylethyl isocyanate. In addition, 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 represented by the "double bond equivalent" of the obtained resin. The double bond equivalent is a standard for the amount of double bonds contained in the molecule. When the photosensitive resin having the same molecular weight is used, the smaller the value of the double bond equivalent is, the larger the amount of introduction of the double bond is.

[double bond equivalent] = [molecular weight of repeating structural unit] / [number of double bonds in repeating structural unit]

The (G) resin of the present invention preferably has a double bond equivalent weight of from 200 to 2,000, more preferably from 300 to 900. When the double bond equivalent of the (G) resin is less than 200, the ratio of the polymerizable monomer (p) into which the ethylenically unsaturated double bond is introduced becomes high, and a sufficient amount of the polymerizable monomer which maintains various properties cannot be obtained (q) ) Copolymerization. In the case of more than 2,000, the number of ethylenically unsaturated double bonds is small, so that sufficient sensitivity cannot be obtained.

Further, the weight average molecular weight (Mw) of the (G) resin is preferably from 2,000 to 200,000, more preferably from 5,000 to 50,000, in terms of good dispersibility of the composition of the present invention.

The reaction of the copolymer (a) with the compound (b) having a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond can be carried out by a known method, and for example, refer to JP-A-2005-156930. The description of paragraph 0016 is incorporated into the present specification.

When the composition of the present invention contains (G) a resin having a polymerizable double bond in a side chain, the content of the resin having a polymerizable double bond in the side chain of (G) is preferably 10% by mass based on the resin component. ~100% by mass, more preferably 20% by mass to 90% by mass, and further preferably 30% by mass to 80% by mass.

(G) The resin having a polymerizable double bond in the side chain may be contained in the composition of the present invention alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

- alkali soluble resin -

The composition of the present invention may further contain an alkali-soluble resin as a binder. Further, the alkali-soluble resin described herein does not include a component contained in the composition of the present invention as a dispersant component.

The alkali-soluble resin can be appropriately selected from the following alkali-soluble resins, which are linear organic high molecular polymers, and are molecules (preferably molecules having an acrylic copolymer or a styrene copolymer as a main chain). There is at least one group that promotes alkali solubility. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic acid/acrylamide copolymer resin is preferred in terms of controlling developability. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

Examples of the group which promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group and the like, and are preferably soluble in an organic solvent and can be developed with a weakly basic aqueous solution. As a particularly preferable one, a (meth)acrylic group is mentioned. These acid groups may be used alone or in combination of two or more.

Examples of the monomer which can give an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate. A monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate or the like. These monomers for introducing an acid group may be used alone or in combination of two or more. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as "a monomer for introducing an acid group") may be used. The polymerization may be carried out as a monomer component.

In the case where a monomer capable of imparting an acid group after polymerization is introduced as a monomer component, it is necessary to carry out a treatment for imparting an acid group as described later after the polymerization.

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

The linear organic high molecular polymer which can be used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a butenoic acid copolymer. , an alkali-soluble phenol resin such as a maleic acid copolymer, a partially esterified maleic acid copolymer, a novolac type resin, or the like, and an acidic cellulose derivative having a carboxylic acid in a side chain, and an addition to a polymer having a hydroxyl group Anhydride is the only one. In particular, copolymers of (meth)acrylic acid with other monomers copolymerizable therewith are suitable as alkali-soluble resins. Other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and vinyl compound. Wait. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate , (methyl) methacrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.; examples of the vinyl compound: styrene, α-methyl styrene, vinyl toluene, methacrylic acid Glycidyl ester, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., Japanese Patent Laid-Open 10 N-phenylmaleimide, N-cyclohexylmaleimide, which is a N-substituted maleimide monomer described in the publication No. -300922. Further, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

The alkali-soluble resin preferably contains a polymer (a) which is a single compound (hereinafter sometimes referred to as "ether dimer") which is required to be represented by the following formula (ED). The body composition is polymerized.

In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

Thereby, the colored composition of the present invention can form a cured coating film which is extremely excellent in heat resistance and transparency. In the above formula (ED) of 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, and examples thereof include methyl group and ethyl group. Linear or branched alkyl such as n-propyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl or 2-ethylhexyl An aryl group such as a phenyl group; an alicyclic ring such as a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group or a 2-methyl-2-adamantyl group; An alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these, in particular, in terms of heat resistance, a substituent of a primary or secondary carbon which is not easily removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is preferable.

Specific examples of the ether dimer include, for example, dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate (dimethyl-2,2'-[oxybis(methylene) )]bis-2-propenoate), diethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxo Bis(methylene)]bis-2-acrylate, di(isopropyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(n-butyl)- 2,2'-[oxobis(methylene)]bis-2-acrylate, di(isobutyl)-2,2'-[oxobis(methylene)]bis-2-acrylate , bis(tert-butyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(third pentyl)-2,2'-[oxo double (Asia Methyl)]bis-2-acrylate, bis(stearyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(lauryl)-2,2' -[oxobis(methylene)]bis-2-acrylate, di(2-ethylhexyl) -2,2'-[oxobis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxo-bis(methylene) Bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl-2,2'- [Oxobis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxobis(methylene)]bis-2-acrylate, dicyclohexyl-2,2 '-[Oxobis(methylene)]bis-2-acrylate, bis(t-butylcyclohexyl)-2,2'-[oxobis(methylene)]bis-2-acrylate , bis(dicyclopentadienyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(tricycloindenyl)-2,2'-[oxo double (methylene)]bis-2-acrylate, bis(isobornyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, diamantyl-2,2 '-[Oxobis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxobis(methylene)]-di- 2-acrylate and the like. Among these, dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxo-bis(methylene) )] bis-2-acrylate, dicyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxo double (Asia Methyl)] bis-2-acrylate. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the above formula (ED) may also copolymerize other monomers.

Further, in order to improve the crosslinking efficiency of the colored composition of the present invention, an alkali-soluble resin having a polymerizable group may also be used. The alkali-soluble resin having a polymerizable group is preferably an alkali-soluble resin containing an allyl group, a (meth)acrylic group, an allyloxyalkyl group or the like in a side chain. Examples of the polymerizable group-containing polymer include Dainal NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (COOH-containing polyurethane oligoacrylate) Gather Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd., Biscoat R-264, KS Resist 106 (both Osaka Organic) Chemical Industry Co., Ltd.), Cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (Malaysia UCB shares) Ltd. manufactured) and so on. The alkali-soluble resin containing a polymerizable group is preferably a resin containing a polymerizable double bond modified by a urethane, which is left by reacting an isocyanate group with an OH group in advance. An unreacted isocyanate group and a (meth)acryloyl group-containing compound and a reaction with a carboxyl group-containing acrylic resin; and an unsaturated group-containing acrylic resin which is a carboxyl group-containing acrylic resin and A reaction obtained by reacting a compound having an epoxy group and a polymerizable double bond in an molecule; an acid side-position epoxy acrylate resin; an acrylic resin containing a polymerizable double bond, which is an OH group-containing acrylic resin a resin obtained by reacting a dibasic acid anhydride having a polymerizable double bond; a resin obtained by reacting an OH group-containing acrylic resin, an isocyanate, and a polymerizable group; and Japanese Patent Laid-Open Publication No. 2002-229207 and Japanese Patent No. A resin or the like obtained by subjecting a resin to an alkali treatment, which has a halogen atom or a sulfonate at the α-position or the β-position on the side chain, as described in JP-A-2003-335814. An ester group such as an acid ester group or the like.

The alkali-soluble resin is particularly preferably a benzyl (meth)acrylate/(meth)acrylic copolymer or a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. In addition, a method of copolymerizing 2-hydroxyethyl methacrylate may be mentioned. 2-Hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3 acrylate, as described in Japanese Laid-Open Patent Publication No. Hei. 7-145. -Phenoxypropyl ester / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methacrylic acid Ester/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, etc., especially benzyl methacrylate/methyl Acrylic copolymer and the like.

The content of the alkali-soluble resin can be referred to in the following paragraphs 0558 to 5571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099; Incorporated into the specification of the present application.

Further, it is preferable to use the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 described in JP-A-2012-32767, and the alkali-soluble resin used in the examples, and Japanese Patent Laid-Open No. 2012-208474 The adhesive resin described in Paragraph No. 0088 to Paragraph No. 0098 of the publication and the adhesive resin described in the example, and the adhesive resin described in Paragraph No. 0022 to Paragraph No. 0032 of JP-A-2012-137531 The adhesive resin used in the example, the adhesive resin described in Paragraph No. 0132 to Paragraph No. 0143 of the Japanese Patent Laid-Open Publication No. 2013-024934, and the adhesive resin used in the Example, Japanese Patent Laid-Open No. 2011-242752 Paragraph No. 0092 to Paragraph No. 0098 and the adhesive resin described in the examples, and the adhesive resin described in Paragraph No. 0030 to Paragraph No. 0072 of JP-A-2012-032770. Inside The contents are incorporated into the specification of the present application. More specifically, the following resins are preferred.

[化59]

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

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

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

The composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

-Organic solvents-

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

The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the colored photosensitive resin composition, and is particularly preferably in consideration of solubility in an ultraviolet absorber, an alkali-soluble resin, a dispersant, or the like. Choose sex and safety. Further, in the preparation of the composition of the present invention, it is preferred to contain at least two organic solvents.

The organic solvent may preferably be exemplified as esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, butyrate B. Ester, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methyl methoxyacetate, A) Ethyl oxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (eg 3- Methyl oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, etc.), alkyl 2-oxopropionate (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.) (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethyl 2-ethoxypropionate Ester)), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropanoate (for example methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate , 2-oxobutyric acid ethyl ester, etc.; and as ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, B Base 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, etc.; and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; and as aromatic hydrocarbons such as toluene, xylene, etc. .

From the viewpoint of improving the solubility of the ultraviolet absorber and the alkali-soluble resin, the surface state of the coating, and the like, it is preferred to mix the organic solvents in two or more kinds. In this case, a mixed solution composed of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve is particularly preferred. Acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Kikabi alcohol 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 content concentration of the composition is from 5% by mass to 80% by mass, and more preferably from 5% by mass to 60% by mass. , particularly preferably from 10% by mass to 50% by mass.

-crosslinker -

It is also possible to supplement the use of the crosslinking agent in the composition of the present invention to further increase the hardness of the cured film obtained by curing the composition.

The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a selected from the group consisting of a methylol group, an alkoxymethyl group, and an anthracene oxygen group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent in the methyl group; (c) at least one selected from the group consisting of a methylol group, an alkoxymethyl group and a decyloxymethyl group A substituted phenol compound, a naphthol compound or a hydroxy hydrazine compound. Among them, a polyfunctional epoxy resin is preferred.

For details of specific examples of the crosslinking agent, the descriptions of paragraphs 0134 to 0147 of JP-A-2004-295116 can be referred to.

When the crosslinking agent is contained in the composition of the present invention, the amount of the crosslinking agent to be added is not particularly limited, but is preferably 2% by mass to 30% by mass, and more preferably 3% by mass, based on the total solid content of the composition. ~20% by mass.

The composition of the present invention may contain only one type of crosslinking agent, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

- Polymerization inhibitors -

In the composition of the present invention, in order to prevent unwanted thermal polymerization of the polymerizable compound during or during storage of the composition, it is desirable to add a small amount of polymerization. Inhibitor.

The polymerization inhibitor which can be used in the present invention may, for example, be hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-Asia Nitrophenylhydroxylamine sulfonium salt and the like.

In the case where the composition of the present invention contains a polymerization inhibitor, the amount of the polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the mass of all the components. The composition of the present invention may contain only one polymerization inhibitor, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

- surfactant -

In the composition of the present invention, various surfactants may be added 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 an anthrone-based surfactant can be used.

In particular, since the composition of the present invention contains a fluorine-based surfactant, the solution characteristics (especially fluidity) at the time of preparation of the coating liquid are further improved, so that the uniformity of the coating thickness or the liquid-saving property can be further improved.

In other words, when the film formation is carried out using a coating liquid using a composition containing a fluorine-based surfactant, the interfacial tension of the surface to be coated and the coating liquid is lowered to wet the coated surface. It is improved and the coating property to the coated surface is improved. Therefore, even when a film of a few micrometers (μm) is formed with a small amount of liquid, it is possible to more preferably form a film having a uniform thickness having a small thickness unevenness, and in this respect, effective.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing surfactant is effective in the uniformity of the thickness of the coating film or the liquid-saving property in the range of the fluorine-based surfactant, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac F141. , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above produced by Di Aisheng (DIC)), Fluorad FC430, Fu Fluorad FC431, Fluorad FC171 (above Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC -383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, propoxylated glycerin, ethoxylated glycerin). Etc.), polyoxyethylene ethyl lauryl ether, polyoxygen Stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Distearate, sorbitan fatty acid ester (Pluronic L10, Pluronic L31, Pluronic L61, Pluronic L62, Pronk, manufactured by BASF) (Pluronic) 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901 , Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol, etc.).

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). , (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (Kyoeisha Chemicals ( () manufacturing), W001 (Yu Shang (share) manufacturing) and so on.

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

Examples of the fluorenone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, and East, manufactured by Toray-Dow Corning Co., Ltd. Toray Silicone DC11PA", "Toray Silicone SH21PA", "Torayone (Toray) Silicone) SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", Momentive Performance Materials "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by the company, "KP341", "KF6001" and "KF6001" manufactured by Shin-Etsu Chemical Co., Ltd. KF6002", BYK Chemie manufactures "BYK 307", "BYK" 323", "BYK" 330 and so on.

The surfactant may be used alone or in combination of two or more.

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

The composition of the present invention may contain only one type of surfactant, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

-Other additives -

In the composition of the present invention, various additives such as a filler, a adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent and the like may be blended as needed. The additives are described in paragraphs 0155 to 0156 of JP-A-2004-295116.

The composition of the present invention may contain the sensitizer or light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the publication.

Specifically, the ultraviolet absorber is preferably the following compound.

--Organic carboxylic acid, organic carboxylic anhydride --

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

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid or an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, and oxalic acid, malonic acid, and amber. Dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, etc. Tricarboxylic acid such as 2,3-propanetricarboxylic acid or aconitic acid. Further, examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group such as benzoic acid or phthalic acid is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a carboxyl group via a phenyl group. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable, and specific examples thereof include maleic acid, malonic acid, succinic acid, and itaconic acid.

Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and Malay. Anhydride, citraconic anhydride, itaconic anhydride, An aliphatic carboxylic anhydride such as glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride or 5-norbornene-2,3-dicarboxylic anhydride. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable, and specifically, for example, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

When the organic carboxylic acid or the organic carboxylic acid anhydride is contained in the composition of the present invention, the amount of the organic carboxylic acid and/or the organic carboxylic acid anhydride is usually 0.01% by mass to 10% by mass based on the total solid content. It is in the range of 0.03 mass% to 5% by mass, more preferably 0.05 mass% to 3% mass%.

By adding these organic carboxylic acids and/or organic carboxylic anhydrides having a molecular weight of 1,000 or less, high pattern adhesion can be maintained, and the residual of the composition can be further reduced.

<Method for Preparing Colored Photosensitive Resin Composition>

The composition of the present invention is prepared by mixing the ingredients described above.

Furthermore, in the preparation of the composition, the components constituting the composition may be formulated at one time, or the components may be dissolved. Disperse in a solvent and then mix them one by one. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all ingredients can be dissolved at the same time. The composition is prepared by dispersing in a solvent, and if necessary, the components may be appropriately prepared into two or more kinds of solutions. The dispersion was mixed and prepared at the time of use (at the time of coating) to prepare a composition.

The composition prepared as described above can be subjected to filtration using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, more preferably a pore diameter of 0.05 μm to 0.5 μm. For later use.

Since the composition of the present invention can form a cured film excellent in heat resistance and color characteristics, it can be preferably used for forming a colored pattern (colored layer) of a color filter. Further, the composition of the present invention can be preferably used for forming a coloring pattern such as a color filter used in an image display device such as a solid-state imaging device (for example, CCD, CMOS, or the like) or a liquid crystal display device (LCD). Further, it can also be preferably used for production of printing inks, inkjet inks, paints, and the like. Among them, it can be preferably used for the production of color filters for solid-state imaging devices such as CCDs and CMOSs.

<Method for Producing Cured Film, Pattern Forming Method, Color Filter, and Color Filter>

Next, the colored cured film, the pattern forming method, and the color filter of the present invention will be described in detail.

The pattern forming method of the present invention includes the steps of: forming a photosensitive resin composition layer forming step, and applying the colored photosensitive resin composition of the present invention to a support to form a colored photosensitive resin composition layer (hereinafter also referred to as " a coloring composition layer"); an exposure step of exposing the colored composition layer to a pattern; and a pattern forming step of developing and removing the unexposed portion to form a colored pattern.

The pattern forming method of the present invention can be preferably applied to forming a coloring pattern (pixel) which the color filter has.

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 that can be applied to pattern formation, other than 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 by a method of producing a color filter for a solid-state image sensor, but the present invention is not limited to this method.

The method for producing a color filter of the present invention employs the pattern forming method of the present invention, comprising the step of forming a colored pattern on a support using the pattern forming method of the present invention.

That is, the method for producing a color filter of the present invention is applied to the pattern forming method of the present invention, and is characterized in that it comprises the steps of applying the colored photosensitive resin composition of the present invention to a support to form a colored photosensitive resin. a step of exposing the colored photosensitive resin composition layer to a pattern; and a step of developing and removing the unexposed portion to form a colored pattern. Further, a step of baking the colored photosensitive resin composition layer (prebaking step) and a step of baking the developed colored pattern (post baking step) may be provided as needed. Hereinafter, these steps are collectively referred to as a pattern forming step.

The color filter of the present invention can be preferably obtained by the above manufacturing method.

Hereinafter, the color filter for a solid-state imaging device may be simply referred to as a "color filter".

Hereinafter, each step of the pattern forming method of the present invention will be described in detail by the method of producing the color filter of the present invention.

<Step of Forming Colored Photosensitive Resin Composition Layer>

In the step of forming the colored photosensitive resin composition layer, the composition of the present invention is applied to a support to form a colored photosensitive resin composition layer.

For the support which can be used in this step, for example, a substrate (for example, a germanium substrate) may be provided with a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS). A substrate for a solid-state image sensor of an element (light receiving element).

The colored pattern of the present invention can be formed on the imaging element forming surface side (surface) of the solid-state imaging device substrate, or can be formed on the surface side (back surface) where the imaging element is not formed.

A light shielding film may be provided between the colored patterns of the solid-state image sensor or the back surface of the solid-state image sensor substrate.

Further, on the support, an undercoat layer may be provided as needed to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate.

Various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be applied to the method of applying the composition of the present invention to a support.

The drying (prebaking) of the colored photosensitive composition layer coated on the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using a hot plate, an oven or the like.

<<Step of exposing the coloring photosensitive composition layer into a pattern (in the case of pattern formation by photolithography)>> - Exposure step -

In the exposure step, for example, using a exposure device such as a stepper, a mask having a predetermined mask pattern is interposed, and the coloring photosensitive composition layer forming step is formed. The photosensitive composition layer is subjected to pattern exposure. Thereby, a cured film can be obtained.

In particular, it is preferable to use ultraviolet rays (particularly i-rays) such as g-rays and i-rays for radiation (light) which can be used for exposure. Irradiation amount (exposure amount) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 1000mJ / cm} 2, most preferably ^{80mJ / cm 2 ~ 500mJ / cm} 2.

The film thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, still more preferably 0.2 μm to 0.8 μm.

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

Further, in this step, a cured film having a thin film thickness of 0.7 μm or less can be preferably formed, and the obtained cured film can be developed by a pattern forming step to be described later, thereby obtaining developability even for a film. A coloring pattern excellent in surface roughness suppression and pattern shape.

<<<Steps for forming a colored pattern>>>

Then, an alkali development treatment is performed, whereby the colored photosensitive composition layer of the portion which is not irradiated with light in the exposure step is eluted into the alkaline aqueous solution, and only the photocured portion remains.

The developer is desirably an organic alkali developer which does not cause damage to the underlying imaging element or circuit. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds. In order to further remove the residue, in recent years, it has been carried out for 120 seconds to 180 seconds. Further, in order to further improve the residue removal property, the following steps may be repeated several times: the developer is removed every 60 seconds, and the supply is further re-applied. Shadow liquid.

Examples of the alkaline agent used in the developing solution include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. An organic basic compound such as a amide, a benzyltrimethylammonium hydroxide, a choline, a pyrrole, a piperidine or a 1,8-diazabicyclo-[5.4.0]-7-undecene, preferably An alkaline aqueous solution obtained by diluting the alkali agent so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is used as a developing solution.

Further, an inorganic base may be used in the developer. The inorganic base is preferably, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate or sodium metasilicate.

Further, in the case of using a developing solution containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

Then, it is preferred to carry out heat treatment (post-baking) after drying. If a color pattern of a plurality of colors is formed, the steps may be repeated one by one for each color to produce a hardened film. Thereby, a color filter can be obtained.

The post-baking is a heat treatment after development for complete hardening, and is usually performed at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C.

The post-baking of the developed coating film may be carried out in a continuous or batch manner by using a heating mechanism such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating machine in such a manner as to achieve the above conditions. Baked.

<<Step of Forming Photoresist Layer, Step of Obtaining Resist Pattern, and Step of Performing Dry Etching (When Patterning Is Performed by Dry Etching)>>

Dry etching can be performed using the patterned photoresist layer as a mask using an etching gas. Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer obtained by curing the colored photosensitive resin composition layer, and dried to form a photoresist layer. At the time of formation of the photoresist layer, it is preferred to further carry out the prebaking treatment. The formation process of the photoresist layer is particularly preferably a form in which heat treatment (Post-Exposure Bake (PEB)) after exposure and heat treatment (post-baking treatment) after development are performed.

For the photoresist, for example, a positive type radiation sensitive composition can be used. The positive radiation sensitive composition can be used for inductive ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays. A resist type positive resist composition. In the radiation, it is preferably g-ray, h-ray, or i-ray, and among them, i-ray is preferable.

Specifically, the positive radiation sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. A positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin is obtained by decomposing a quinonediazide group by light irradiation at a wavelength of 500 nm or less to produce a carboxyl group, and the result is changed from an alkali-insoluble state. Alkali soluble. Since the positive resist has an excellent resolving power, it can be used to form an integrated circuit such as an integrated circuit (IC) or a large scale integrated circuit (LSI). The quinonediazide compound may be a naphthoquinonediazide compound. For example, "FHi622BC" (made by Fujifilm Electronic Materials Co., Ltd.), etc. are mentioned as a commercial item.

The thickness of the photoresist layer is preferably from 0.1 μm to 3 μm, preferably from 0.2 μm to 2.5. Μm, and further preferably 0.3 μm to 2 μm. Furthermore, the formation of the coated photoresist layer can be preferably carried out using the coating method of the coloring layer described above.

Then, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a resist through-hole group. The formation of the resist pattern is not particularly limited, and the conventionally known photolithography technique can be appropriately optimized. A resist through-hole group is provided in the photoresist layer by exposure and development, whereby a resist pattern as an etching mask used for subsequent etching is provided on the colored layer.

The exposure of the photoresist layer can be performed by interposing a predetermined mask pattern, and using a g-ray, an h-ray, an i-ray, or the like, preferably an i-ray, for a positive or negative radiation sensitive composition. exposure. After the exposure, the photoresist is removed by performing development processing using a developer to correspond to a region where the colored pattern is to be formed.

The developer may be used as long as it does not affect the coloring layer containing the coloring agent, and the exposed portion of the positive resist and the uncured portion of the negative resist may be used. For example, various organic solvents may be used. Combination or alkaline aqueous solution. The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound in a concentration of from 0.001% by mass to 10% by mass, preferably from 0.01% by mass to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and the like. Further, when an alkaline aqueous solution is used as the developing solution, the cleaning treatment is usually performed by water after development.

Then, the resist pattern is used as an etching mask, and patterning is performed by dry etching so that the through-hole group is formed in the colored layer. Thereby a colored pattern is formed. The through hole group is disposed in the colored layer in a checkerboard pattern. 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 checkerboard pattern.

From the viewpoint of forming the pattern cross section closer to a rectangular shape or further reducing damage to the support, dry etching is preferably performed in the following form.

It is preferable to include a first-stage etching, a second-stage etching, and an over-etching. The first-stage etching uses a mixed gas of a fluorine-based gas and oxygen (O ₂ ), and etching is performed until the support is not exposed. In the region (depth), the second-stage etching is performed after the etching in the first step, and etching is performed using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) until it is preferable that the support is exposed. The over-etching is performed after the support is exposed, in the vicinity of (depth). Hereinafter, a specific method of dry etching, etching in the first stage, etching in the second stage, and over etching will be described.

Dry etching is performed by previously obtaining etching conditions by the following method.

(1) The etching rate (nm/min) of the etching in the first stage and the etching rate (nm/min) in the etching in the second stage were respectively calculated. (2) Calculate the time required for etching in the etching of the first stage and the time required to etch the required thickness in the etching of the second stage. (3) The first-stage etching is performed in accordance with the etching time calculated in the above (2). (4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Or, by the end point detection to determine the etching time, according to The etching of the second stage is performed by the determined etching time. (5) The overetching time is calculated for the total time of the above (3) and (4), and over etching is performed.

The mixed gas used in the first-stage etching step preferably contains a fluorine-based gas and oxygen (O ₂ ) from the viewpoint of processing the organic material as the film to be processed into a rectangular shape. Further, the etching step of the first step can be prevented from being damaged by the support so as to be etched until the region where the support is not exposed. Further, from the viewpoint of avoiding damage of the support, the etching step and the over-etching step in the second step are preferably performed by a mixed gas of a fluorine-based gas and oxygen in the etching step of the first-stage etching step. After the region where the support is not exposed, the etching treatment is performed using a mixed gas of nitrogen gas and oxygen gas.

The ratio of the amount of etching in the etching step in the first step to the amount of etching in the etching step in the second step is important in such a manner as not to impair the squareness obtained by the etching treatment in the etching step of the first step. . Further, the ratio of the latter in the total etching amount (the total of the etching amount in the etching step in the first step and the etching amount in the etching step in the second step) is preferably in a range of more than 0% and not more than 50%. More preferably 10% to 20%. The amount of etching refers to an amount calculated from the difference between the film thickness remaining in the film to be etched and the film thickness before etching.

In addition, the etching preferably includes an overetching process. The overetching treatment is preferably performed by setting an overetch ratio. Further, the overetch ratio is preferably calculated based on the etching processing time that is initially performed. The overetching ratio can be arbitrarily set, and it is preferably 30% or less, more preferably 5% to 25%, of the etching treatment time in the etching step in terms of maintaining the etching resistance of the photoresist and the rectangularity of the etching pattern. , especially good 10% ~ 15%.

Then, the resist pattern remaining after the etching (ie, the etching mask) is removed. The removal of the resist pattern preferably includes the steps of: applying a stripping liquid or a solvent to the resist pattern to adjust the resist pattern to a removable state; and removing the resist pattern using the washing water. step.

The step of applying a peeling liquid or a solvent to the resist pattern to adjust the resist pattern to a removable state includes, for example, applying a peeling liquid or a solvent to at least the resist pattern, and stopping the film for a predetermined period of time. The step of immersing the development. The time for stopping the stripping solution or the solvent is not particularly limited, and is preferably from several tens of seconds to several minutes.

Further, the step of removing the resist pattern using the washing water may, for example, be a step of ejecting the washing water from the resist pattern by a spray type or a spray type spray nozzle to remove the resist pattern. Pure water can be preferably used for the washing water. Further, the injection nozzle may be an injection nozzle that includes the entire support in the injection range thereof, or an injection nozzle that is a movable injection nozzle and whose movable range includes the entire support. When the ejection nozzle is movable, the cleaning water can be sprayed two times or more from the center of the support to the end of the support in the step of removing the resist pattern, thereby more effectively removing the resist pattern. .

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

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, and the like. Diethanolamine, triethanolamine or the like is preferably monoethanolamine, diethanolamine or triethanolamine, more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α-A. Pyridine, β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-dimethylpyridine, 2,6-lutidine, etc., preferably N-methyl-2-pyrrolidone N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The stripping liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine as acyclic nitrogen-containing compound. The nitrogen-containing compound is at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethylmorpholine, and further preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

When the removal is performed by the peeling liquid, the resist pattern formed on the first colored pattern may be removed, and deposits (precipitates) as etching products may be adhered to the side walls of the first colored pattern. In this case, the deposit may not be completely removed. The term "deposited material" means that the etching product adheres to the side wall of the colored layer.

The content of the stripping liquid is preferably 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the stripping liquid, and the content of the cyclic nitrogen-containing compound is 65 parts by mass based on 100 parts by mass of the stripping liquid. More than or equal to 70 parts by mass. Further, the peeling liquid is preferably one obtained by diluting a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

Furthermore, the manufacturing method of the present invention may include a step known as a method of producing a color filter for a solid-state image sensor as a step other than the above. For example, after the coloring photosensitive composition layer forming step, the exposure step, and the pattern forming step, a hardening step of hardening the formed coloring pattern by heating and/or exposure may be included as needed.

Further, in the case of using the composition of the present invention, for example, clogging of the nozzle or the piping portion of the coating device discharge portion or adhesion of the coloring composition or pigment to the coater may occur. settlement. Pollution caused by drying, etc. Therefore, in order to efficiently clean the contamination caused by the composition of the present invention, it is preferred to use a solvent related to the present composition described above as a cleaning liquid. In addition, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The cleaning liquids described in the Japanese Patent Publication No. 2007-291191, the Japanese Patent Publication No. 2007-2101, the Japanese Patent Publication No. 2007-2102, and the Japanese Patent Publication No. 2007-281523 can also be used. It is preferably used for cleaning and removal of the composition of the present invention.

Among them, preferred are alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoesters. Alkyl ether.

These solvents may be used singly or in combination of two or more. In the case of mixing two or more kinds, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. Particularly preferred is a mixed solvent of Propyleneglycol monomethylether acetate (PGMEA) and Propyleneglycol monomethylether (PGME) in a ratio of 60/40. Further, in order to increase the permeability of the cleaning liquid to the contaminants, a surfactant related to the above-described composition may be added to the cleaning liquid.

Since the color filter of the present invention uses the composition of the present invention, it is possible to perform exposure with excellent exposure margin, and the pattern shape of the formed color pattern (colored pixel) is excellent, and the surface of the pattern is rough or developed. Since the residue of the portion is suppressed, the color characteristics are excellent.

The color filter of the present invention can be preferably used for a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for a high-resolution CCD or CMOS of more than one million pixels. The color filter for a solid-state image sensor of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting the CCD or CMOS and a microlens for collecting light.

In addition, the thickness of the colored pattern (colored pixel) of the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less.

In addition, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5. It is preferably not more than μm, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

[Solid image sensor]

The solid-state imaging device of the present invention includes the color filter of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a configuration that functions as a solid-state imaging device, and the configuration is as follows.

The solid-state imaging device has a configuration in which a plurality of photodiodes (photodiodes) constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a polycrystalline germanium or the like are provided on the support. The electrode includes a light-shielding film containing tungsten or the like on the photodiode and the transfer electrode, and the light-receiving portion of the photodiode is opened, and the light-shielding film covers the entire surface of the light-shielding film and the photodiode An element protective film containing tantalum nitride or the like formed in a portion thereof has the color filter for a solid-state imaging device of the present invention on the element protective film.

Furthermore, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the element protective layer and under the color filter (on the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.

[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 including the color filter of the present invention can display a high-quality image in which the hue of the display image is good and the display characteristics are excellent.

The definition of the display device or the details of each display device is described in, for example, "Electronic display device (Sasaki Sasaki, Industrial Research Association, stocks, issued in 1990)", "Display elements (Ibuki Shun, industrial books) (shares), issued in 1989) and so on. In addition, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Editor Uchida Ronjin, Industrial Research Association, issued in 1994)". The liquid crystal display device to which the present invention is 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 can also be used in a liquid crystal display device of a Thin Film Transistor (TFT) type. The liquid crystal display device of the color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to a liquid crystal display device or a super-twisting direction having a viewing angle such as a transverse electric field driving method such as coplanar switching (IPS) or a pixel division method such as multi-domain vertical alignment (MVA). Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching (FFS) and Reflective-Optically Compensated Bend (R-OCB) and the like.

In addition, the color filter of the present invention can also be used in a bright and high-definition Color-filter On Array (COA) mode. In the COA liquid crystal display device, the required characteristics of the color filter layer are the same as described above. In addition to the usual required characteristics, the required characteristics of the interlayer insulating film, that is, the low dielectric constant and the peeling resistance are sometimes required. In the color filter of the present invention, since a dye multimer having excellent hue is used, color purity, light transmittance, and the like are excellent, and color tone (pixel) is excellent in color tone, so that high resolution and long-term durability can be provided. A COA liquid crystal display device excellent in properties. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described, for example, in "Electroluminescence (EL), Plasma Display Panel (PDP), Liquid Crystal Display (LCD) displays - technology and market. Trends - (Toray Research Center, Research and Research Department, issued in 2001), 43 pages, etc.

The liquid crystal display device including the color filter of the present invention comprises, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film. . The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. For example, the "94 liquid crystal display peripheral materials - chemicals market (Ichishima Kentaro, CMC (share), issued in 1994)", "2003 liquid crystal related market status and future prospects (volume) (Former Liangji, Fuji Kamelai Institute (share), issued in 2003).

The backlight is recorded on the 18th page of the December 2005 issue of the "SID meeting Digest" 1380 (2005) (A. Konno et al.) or the monthly "Monitor"~ 24 pages (Island Kang Yu) and the literature 25 to 30 pages (Yumu Longming) and so on.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and the red, green, and blue LED light source can be realized. (RGB-LED) is set as a backlight, and can provide a liquid crystal display device with high brightness and high color reproducibility.

[Examples]

The invention is more specifically illustrated by the following examples. The materials, the amounts, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "%" and "parts" are quality standards unless otherwise specified.

<Synthesis of Dispersant (C-1)>

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 80 parts of methyl methacrylate, 120 parts of ethyl acrylate, and 40 parts of methoxypropyl acetate were added, and the mixture was replaced with nitrogen. The inside of the reaction vessel was heated to 80 ° C, and 4.4 parts of 3-mercapto-1,2-propanediol was added, and then 0.2 part of 2,2'-azobisisobutyronitrile was added thereto 20 times. The reaction was carried out for 12 hours while maintaining the reaction vessel at 80 ° C, and it was confirmed by solid content measurement that 95% had reacted. Then, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added to the reaction. In the latter solution, the reaction was carried out at 120 ° C for 2 hours, followed by reaction at 80 ° C for 5 hours, and titration confirmed 90%. The anhydride is semi-esterified. The obtained resin solution was sampled by 2 g, and dried by heating at 180 ° C for 20 minutes to measure a nonvolatile component. Propylene glycol monomethyl ether acetate was added to the resin solution obtained in advance so that the nonvolatile content was 25% by mass, and the dispersion of the aromatic carboxyl group having an acid value of 44 mg KOH/g and a number average molecular weight of 5,200 in a solid content unit was obtained. Agent (C-1).

<Synthesis of Dispersant (C-2)>

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 160 parts of methyl methacrylate, 40 parts of ethyl acrylate, and 40 parts of methoxypropyl acetate were added, and the mixture was replaced with nitrogen. The inside of the reaction vessel was heated to 80 ° C, and 2.2 parts of 3-mercapto-1,2-propanediol was added, and then 0.2 part of 2,2'-azobisisobutyronitrile was added thereto 20 times. The reaction was carried out for 12 hours while maintaining the reaction vessel at 80 ° C, and it was confirmed by solid content measurement that 95% had reacted. Then, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added to the reaction. After the reaction was carried out at 120 ° C for 2 hours, and then at 80 ° C for 5 hours, it was confirmed by titration that 90% or more of the acid anhydride was half-esterified. The obtained resin solution was sampled at about 2 g, and dried by heating at 180 ° C for 20 minutes to measure a nonvolatile component. Propylene glycol monomethyl ether acetate was added to the resin solution obtained in advance so that the nonvolatile content was 25% by mass, and the dispersion of the aromatic carboxyl group having an acid value of 23 mg KOH/g and a number average molecular weight of 11,000 in a solid content unit was obtained. Solution (C-2) solution.

<Synthesis of Dispersant (C-3)>

Reference is made to the paragraph number 0334 of Japanese Patent Laid-Open Publication No. 2007-277514. Loaded for synthesis.

Dispersant (C-3):

In the chemical formula of the dispersing agent (C-3), a is 2.0, b is 4.0, an acid value is 10 mgKOH/g, and a weight average molecular weight (Mw) is 20,000.

Further, a and b respectively indicate the number of partial structures indicated in parentheses, and satisfy a+b=6.

<Synthesis of Resin Adhesive 1>

A propylene glycol monomethyl ether acetate was placed in a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas introduction tube, and a stirring device, and heated to 100 ° C while introducing nitrogen gas into the reaction vessel. A mixture of 123.3 g of benzyl methacrylate, 25.8 g of methacrylic acid, and 10.0 g of azobisisobutyronitrile was added dropwise from the dropping tube at the same temperature for 1 hour to carry out a polymerization reaction.

After the obtained resin solution was cooled to room temperature, about 3 g was sampled and dried by heating at 180 ° C for 20 minutes to measure a nonvolatile component. A propylene glycol acetate was added to the resin solution which was previously synthesized so that the nonvolatile content was 40% by mass, and a solution of the resin binder 1 was obtained.

<Manufacture of Pigment Dispersion Composition>

The mixture of the following composition is uniformly stirred and mixed, and then mixed by a bead mill. The pigment dispersion composition 1 was prepared by dispersing for 3 hours.

Pigment Derivative (I-1):

<Preparation of Colored Photosensitive Resin Composition>

The mixture of the following composition was uniformly stirred and mixed to prepare a colored photosensitive resin composition.

The colored photosensitive resin composition 2 to the colored photosensitive resin composition 15 were prepared by the same method as the colored photosensitive resin composition 1 except that the composition was changed to the composition of the following Table 1. In addition, the derivative A, the derivative (I-2), the derivative (II-1), and the derivative (II-2) used in the colored photosensitive resin composition 2 to the colored photosensitive resin composition 12 are The following structural formula is shown.

Derivative A (manufactured by Fujifilm Precision Chemical Co., Ltd.):

Derivative (I-2):

Derivative (II-1):

Derivative (II-2):

<evaluation> <<residue>>

The colored photosensitive resin compositions of the examples and the comparative examples obtained above were applied onto a ruthenium wafer with an undercoat layer by a spin coater at a film thickness of 0.8 μm, using 100 ° C. The hot plate was heat treated for 120 seconds (prebaking).

Then, using an i-ray stepwise exposure apparatus FPA-3000i5+ (manufactured by Canon), a 1.4 μm square Bayer pattern was masked at a wavelength of 365 nm so that the pattern size became 1.4 μm square. Adjust the exposure to expose.

Thereafter, a glass wafer on which an exposed coating film was formed was subjected to dip development at 23 ° C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, it was rinsed using a rotary shower, washed with pure water, and subjected to heat treatment (post-baking) for 300 seconds using a hot plate at 200 ° C to obtain a monochromatic color in which a Bell pattern of 1.4 μm square was formed. Filter.

The obtained 1.4 μm square Bell pattern was observed by Scanning Electron Microscopy (SEM) (S-4800, manufactured by Hitachi, Ltd.), and the residue around the pattern was observed to evaluate the goodness of the lithography.

~Judgement benchmark~

5: No residue was observed.

4: A slight residue was observed.

3: Residue was observed, but it was a practically problem-free level.

2: The residue was observed to be an impractical level.

1: Residue was observed on one side of the substrate around the pattern.

<<pattern linearity>>

The pattern substrate obtained above was observed from the upper side using a length measuring SEM (S-4800, manufactured by Hitachi, Ltd.).

~Judgement benchmark~

5: One side of the pattern is a straight line as shown in Fig. 1(a).

4: The angle of the pattern is slightly round as shown in Fig. 1(b).

3: The side of the pattern is slightly round as shown in Fig. 1(c).

2: The pattern is rounded as shown in (d) of Fig. 1.

1: The pattern is circular as shown in Fig. 1(e).

<<stability>>

The change in viscosity of the colored photosensitive resin composition of the examples and the comparative examples obtained above obtained at room temperature for 3 months was evaluated.

5: The viscosity change before and after the passage was 3.0% or less.

4: The viscosity change before and after the time exceeded 3.0% and was 5.0% or less.

3: The viscosity change before and after the time exceeded 5.0% and was 10.0% or less.

2: The viscosity change before and after the time exceeded 10.0% and was 30.0% or less.

1: The viscosity change before and after the passage exceeded 30.0%.

<<Brightness uneven>>

The colored photosensitive resin compositions of the examples and the comparative examples obtained above were applied onto a glass substrate so as to have a film thickness after drying of 0.8 μm by a spin coater, and prebaked at 100 ° C for 120 seconds. A colored coating film was obtained.

Each of the obtained colored coating films was placed between an observation lens of an optical microscope and a light source, and the light was irradiated toward the observation lens, and the transmitted light state was observed using an optical microscope provided with a digital camera having a magnification of 1,000. A CCD of 1.28 million pixels was mounted on a digital camera provided in an optical microscope, and the surface of the colored coating film in a transmitted light state was imaged by the digital camera. The captured image is stored as a digital image (digital image) which is digitally converted in the form of a bit map of 8 bits.

Further, the filming of the surface of the film of the colored coating film was performed on arbitrarily selected 20 regions. Further, regarding the digitally converted data, the luminance of each of the RGB three primary colors is quantized and stored for the captured image with a density distribution of 256 levels of 0 to 255.

Then, the stored digital image is divided into a lattice shape so that one grid size corresponds to 0.5 μm square on the actual substrate, and the luminance in one block is averaged. In the present embodiment, a digital camera of 1.28 million pixels is used to capture an image 1000 times optically, so 0.5 μm on the actual substrate becomes 0.5 mm on the captured image, and the image size on the display is 452 mm × 352 mm. Therefore, the total number of blocks in a region is 636,416.

For all blocks of each region, the average brightness of any one block and all adjacent blocks adjacent thereto is measured. A block having a difference of 5% or more from the average luminance of the adjacent blocks is regarded as a significant difference block, and an average total number of significant difference blocks of the entire area is calculated. The smaller the value is, the smaller the difference in density from the adjacent blocks is, and the less the unevenness in luminance is, the more excellent the characteristics as a color filter are.

~Judgement benchmark~

5: The number of significant differences is less than 2000.

4: The number of significant differences is 2001~3000.

3: The number of significant differences is 3001~5000.

2: The number of significant differences is 5001~10000.

1: The number of significant difference blocks is 10001 or more.

In the above Table 1, each symbol means the following compound.

PG58: zinc halide phthalocyanine pigment (C.I. Pigment Green 58)

PY139: Isoporphyrin yellow pigment (C.I. Pigment Yellow 139)

PY150: Nickel azo yellow pigment (C.I. Pigment Yellow 150)

PY185: Isoporphyrin yellow pigment (C.I. Pigment Yellow 185)

PG36: Copper phthalocyanine pigment (C.I. Pigment Green 36)

Unsubstituted Zn Phthalocyanine Pigment: Unhalogenated Zinc Phthalocyanine Pigment

From the results shown in Table 1, it was found that when non-halide zinc phthalocyanine or copper halide phthalocyanine was used as the phthalocyanine pigment (Comparative Example 1 to Comparative Example 5), the pattern linearity, stability, and brightness were not Both are greatly degraded. Further, when the pigment derivative or the dispersant used in the present invention was not used (Comparative Example 4 to Comparative Example 5), the lithography, pattern linearity, stability, and luminance unevenness were greatly deteriorated.

On the other hand, for example, the photosensitive resin composition of the present invention shown in the examples contains (A) a zinc halide phthalocyanine pigment and (B) a pigment derivative having a specific structure as essential components in the composition of the present invention. Therefore, lithography, pattern linearity, stability and brightness unevenness have been greatly improved.

Claims (16)

A colored photosensitive resin composition comprising: (A) a zinc halide phthalocyanine pigment, (B-1) a dye derivative represented by the following formula (I), and/or (B-2) a general formula ( II) a pigment derivative, (C) a dispersant, (D) a photopolymerization initiator, and (E) a polymerizable compound, wherein the content of the (C) dispersant is 20 parts by mass based on 100 parts by mass of the pigment. Parts by mass ~40 parts by mass, In the formula (I), Dye represents an n-valent organic dye residue, and X represents a single bond, -CONH-Y ² -, -SO ₂ NH-Y ² - or -CH ₂ NHCOCH ₂ NH-Y ² -, Y ² represents an alkylene group or an extended aryl group which may have a substituent, and Y ¹ represents -NH- or -O-, and when n represents 1, Z represents a hydroxyl group, an alkoxy group, and the following formula (III) The group represented by -NH-X-Dye, X has the same meaning as X in the formula (I), and when n represents an integer of 2 to 4, Z represents a hydroxyl group, an alkoxy group or the following The group represented by the formula (III), R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero ring containing a nitrogen atom; m represents 1 to 6 An integer, n represents an integer from 1 to 4; when n is 2 or more, a plurality of X, Y ¹ , R ¹ and R ² may be the same or different; In the formula (III), Y ³ represents -NH- or -O-; R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero atom containing a nitrogen atom; Ring; m represents an integer from 1 to 6; In the general formula (II), Dye represents quinophthalone residue having a substituent, X ¹ represents _{-NR'SO 2 -, - SO 2 NR} '-, - CONR' -, - CH 2 NR'COCH 2 NR '- or -NR'CO-, X ² represents a aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaromatic ring group having 4 to 20 carbon atoms which may have a substituent, and these groups are also It may be bonded to each other via a divalent linking group selected from -NR'-, -O-, -SO ₂ - or -CO-; X ³ represents -NR'- or -O-; R' represents a hydrogen atom, The alkyl group having a carbon number of 1 to 20 having a substituent, 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; A and B are respectively selected a group represented by the following formula (1), a group represented by the following formula (2), -O-(CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ¹¹ ,- a group in Cl, -F and -X ³ -X ² -X ¹ -Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, and R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, and may have The substituent has an alkyl group having 1 to 20 carbon atoms, 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, and n represents an integer of 0 to 20 Any one of A and B is a compound of the following formula (1) a group represented by the following formula (2), -O-(CH ₂ ) _n -R ⁸ , -OR ⁹ or -NR ¹⁰ R ¹¹ , t represents an integer of 1 to 3; In the case of 2 or more, a plurality of X ¹ , X ² , X ³ , A, and B may be the same or different; In the formula (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, and a carbon number of 2 to 20 which may have a substituent. An alkenyl group or a aryl group having 6 to 20 carbon atoms which may have a substituent, and these groups may also be divalently selected from -NR'-, -O-, -SO ₂ -, -CO- The linking group is bonded to each other; R' represents 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 carbon number which may have a substituent An aryl group of 6 to 20; R ¹ and R ² each independently represent 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 are} also The heterocyclic structure may be formed integrally, and the heterocyclic ring structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, or may have a substituent; in the formula (2), Z ¹ represents a linking triazine ring and a nitrogen atom. Single bond, -NR'-, -NR'-G-CO-, -NR'-G-CONR"-, -NR'-G-SO ₂ -, -NR'-G-SO ₂ NR"-, -OG-CO-, -OG-CONR'-, -OG-SO ₂ - or -OG-SO ₂ NR'-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and may have a substitution a base having 2 to 20 carbon atoms or may have The substituent has a carbon number of 6 to 20, and R' and R" each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent of 2 to 20 An alkenyl group or an aryl group having 6 to 20 carbon atoms which may have a substituent; and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent 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 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 may have The substituent has an alkenyl group having 2 to 20 carbon atoms. The colored photosensitive resin composition according to claim 1, further comprising a yellow pigment. The colored photosensitive resin composition according to claim 2, wherein the yellow pigment is C.I. Pigment Yellow 150 and/or C.I. Pigment Yellow 185. The colored photosensitive resin composition according to claim 1, wherein the (C) dispersing agent is the hydroxyl group of the vinyl polymer having a hydroxyl group at a single terminal and a tricarboxylic acid anhydride or a tetracarboxylic acid The anhydride is reacted. The colored photosensitive resin composition according to claim 1, wherein in the formula (I), Dye has a monoazo dye containing a benzimidazolone skeleton. The colored photosensitive resin composition according to claim 1, wherein in the formula (II), the quinophthalone residue is represented by the following formula (II-1), In the formula (II-1), D and E each represent an aromatic group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring bonded to D and E, and a substituent. a cyclic or heterocyclic group, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a carboxyl group or a salt thereof, an ester group having 1 to 20 carbon atoms, a decylamino group having 1 to 20 carbon atoms, an anthracenyl group or a salt thereof, and an amine Any one of a sulfonyl group, a -NR'R"-, or a nitro group; wherein R' and R" each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and may have a substituent The alkenyl group having 2 to 20 carbon atoms or the aryl group having 6 to 20 carbon atoms which may have a substituent; p represents an integer of 0 to 4, q represents an integer calculated by 4-p; * represents a formula The bonding site of X ¹ in II). The colored photosensitive resin composition according to claim 1, wherein in the formula (II), A and B represent a group represented by the formula (1) or the formula (2) The group represented, and A and B are the same group. The colored photosensitive resin composition according to any one of the items 1 to 7, wherein the (A) zinc halide phthalocyanine pigment is C.I. Pigment Green 58. Coloring sensitization as described in any one of claims 1 to 7 The resin composition in which the total amount of the colorant is 40% by mass or more based on all the solid components in the composition. The colored photosensitive resin composition according to any one of the items 1 to 7, which is a colored region for forming a color filter. A cured film obtained by curing the colored photosensitive resin composition according to any one of the first to seventh aspects of the invention. A method of producing a color filter comprising: applying a colored photosensitive resin composition according to any one of claims 1 to 7 to a support to form a colored photosensitive resin composition layer a step of exposing the colored photosensitive resin composition layer to a pattern; and a step of developing and removing the unexposed portion to form a colored pattern. A method of producing a color filter comprising: applying a colored photosensitive resin composition according to any one of claims 1 to 7 to a support to form a colored photosensitive resin composition layer a step of hardening to form a color layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and The resist pattern is used as an etch mask to dry etch the colored layer. A color filter which is a color filter having a cured film as described in claim 11 or by the 12th or 13th of the patent application A color filter manufactured by the method for producing a color filter according to the invention. A solid-state image sensor having a color filter as described in claim 14 of the patent application. An image display device having the color filter of claim 14 of the patent application.