JP2023002607A - Coloring photosensitive resin composition, film, color filter, manufacturing method of color filter, structure, solid-state imaging element and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring photosensitive resin composition capable of suppressing generation of layer separation accompanying post exposure transfer, and capable of forming a film excellent in moisture resistance, a film, a color filter, a manufacturing method of the color filter, a structure, a solid-state imaging element and an image display device.

SOLUTION: This coloring photosensitive resin composition contains a coloring material, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent. The photopolymerization initiator includes a photopolymerization initiator a1 having an absorption coefficient of 8×10³ mL/gcm or more at a wavelength of 365 nm in methanol. The resin contains a resin b1 containing a repeating unit derived from a compound represented by formula (I) and a repeating unit derived from an alkyl (meth)acrylate.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to a colored photosensitive resin composition. The present invention also relates to a film using the colored photosensitive resin composition, a color filter, a method for producing a color filter, a structure, a solid-state imaging device, and an image display device.

2. Description of the Related Art In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements. A color filter usually comprises three primary color pixels of red, green and blue and serves to separate the transmitted light into the three primary colors.

Each color pixel of the color filter is manufactured using a colored photosensitive resin composition containing a coloring material, a resin, a polymerizable monomer, a photopolymerization initiator, a solvent, etc., as described in Patent Documents 1 and 2. ing.

JP 2018-45189 A JP 2017-167538 A

In recent years, it has been desired to further improve moisture resistance of films used for color filters and the like. When the present inventor examined the colored photosensitive resin compositions disclosed in Patent Documents 1 and 2, it was found that the level of moisture resistance required in recent years has not been reached and there is room for further improvement. rice field.

Further, when a color filter is produced using a colored photosensitive resin composition, in general, a colored photosensitive resin composition is used to form a colored photosensitive resin composition layer on a support, and a colored photosensitive resin composition is used. It is formed through a step of patternwise exposing the resin composition layer (exposure step) and a step of developing and removing the unexposed portions of the colored photosensitive resin composition layer to form a pattern (pixels) (development step). be. Depending on manufacturing conditions, etc., the colored photosensitive resin composition layer after exposure may be left for a long period of time and then subjected to a development step to form a pattern (pixels). According to the studies of the present inventors, it was found that when the colored photosensitive resin composition layer after exposure is left for a long time, layer separation may occur in the exposed area, resulting in color unevenness, defects, and the like. .

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a colored photosensitive resin composition capable of suppressing the occurrence of layer separation associated with exposure after exposure and forming a film having excellent moisture resistance. Another object of the present invention is to provide a film, a color filter, a method for producing a color filter, a structure, a solid-state imaging device, and an image display device using this colored photosensitive resin composition.

式中、Ｘ^１は、ＯまたはＮＨを表し、Ｒ^１は水素原子またはメチル基を表し、Ｌ^１は２価の連結基を表し、Ｒ^１０は置換基を表し、ｍは０～２の整数を表し、ｐは１以上の整数を表す。
＜２＞ 式（Ｉ）で表される化合物が下記式（Ｉ－１）で表される化合物である、＜１＞に記載の着色感光性樹脂組成物；

式中、Ｘ^１は、ＯまたはＮＨを表し、Ｒ^１は水素原子またはメチル基を表し、Ｒ^２、Ｒ^３およびＲ^１１はそれぞれ独立して炭化水素基を表し、Ｒ^１２は置換基を表し、ｎは０～１５の整数を表し、ｍは０～２の整数を表し、ｐ１は０以上の整数を表し、ｑ１は１以上の整数を表す。
＜３＞ 樹脂ｂ１は、全繰り返し単位中に繰り返し単位ｂ１－１を１～７０モル％、繰り返し単位ｂ１－２を１～７０モル％含有する、＜１＞または＜２＞に記載の着色感光性樹脂組成物。
＜４＞ 樹脂は、更に、芳香族カルボキシル基を有する樹脂ｂ２を含む、＜１＞～＜３＞のいずれかに記載の着色感光性樹脂組成物。
＜５＞ 樹脂ｂ２は下記式（ｂ２－１）で表される繰り返し単位を含む樹脂である、＜４＞に記載の着色感光性樹脂組成物；

式中、Ａｒ^１は芳香族カルボキシル基を含む基を表し、Ｌ^１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ^２は、２価の連結基を表す。
＜６＞ 色材は顔料を含む、＜１＞～＜５＞のいずれかに記載の着色感光性樹脂組成物。
＜７＞ 顔料は、ジケトピロロピロール化合物およびフタロシアニン化合物から選ばれる少なくとも１種を含む、＜６＞に記載の着色感光性樹脂組成物。
＜８＞ 重合性モノマーは酸基を有する重合性モノマーを含む、＜１＞～＜７＞のいずれかに記載の着色感光性樹脂組成物。
＜９＞ カラーフィルタ用である、＜１＞～＜８＞のいずれかに記載の着色感光性樹脂組成物。
＜１０＞ 固体撮像素子用である、＜１＞～＜９＞のいずれかに記載の着色感光性樹脂組成物。
＜１１＞ 隔壁で区画された領域に着色層を形成するために用いられる、＜１＞～＜１０＞のいずれかに記載の着色感光性樹脂組成物。
＜１２＞ ＜１＞～＜１１＞のいずれかに記載の着色感光性樹脂組成物から得られる膜。
＜１３＞ ＜１＞～＜１１＞のいずれかに記載の着色感光性樹脂組成物から得られるカラーフィルタ。
＜１４＞ ＜１＞～＜１１＞のいずれかに記載の着色感光性樹脂組成物を用いて支持体上に着色感光性樹脂組成物層を形成する工程と、フォトリソグラフィ法により着色感光性樹脂組成物層に対してパターンを形成する工程と、を有するカラーフィルタの製造方法。
＜１５＞ 支持体と、
支持体上に設けられた隔壁と、
支持体上であって、隔壁で区画された領域に設けられた＜１＞～＜１１＞のいずれかに記載の着色感光性樹脂組成物から得られる着色層と、を有する
構造体。
＜１６＞ ＜１２＞に記載の膜を有する固体撮像素子。
＜１７＞ ＜１２＞に記載の膜を有する画像表示装置。 According to the study of the present inventors, a coloring containing a resin b1 containing a repeating unit b1-1 derived from a compound represented by the formula (I) described later and a repeating unit b1-2 derived from an alkyl (meth)acrylate They have found that by using a photosensitive resin composition, it is possible to form a film that is excellent in moisture resistance and that suppresses film shrinkage even when exposed to a high-humidity environment. The reason why such effects are obtained is presumed to be as follows. Since this resin b1 contains the repeating unit b1-1, it is presumed that the interaction between the aromatic rings contained in the unit b1-1 suppressed the film shrinkage. Furthermore, since this resin b1 contains the repeating unit b1-2 derived from an alkyl (meth)acrylate, it is presumed that the film can be appropriately hydrophobized and water is less likely to penetrate into the film. Therefore, it is presumed that a film having excellent moisture resistance could be formed. In addition, the present inventors have further studied the colored photosensitive resin composition using the resin b1, and found that when the colored photosensitive resin composition after exposure is set aside, the exposed portion of the colored photosensitive resin composition is It turned out that it is easy to carry out layer separation. As a result of further studies by the present inventors, in a colored photosensitive resin composition containing resin b1, the absorption coefficient at a wavelength of 365 nm in methanol as a photopolymerization initiator is 8 × 10 ³ mL / gcm or more. By using the initiator a1, even if the colored photosensitive resin composition after exposure is left for a long time, it was found that the exposed part of the colored photosensitive resin composition can suppress layer separation, and the present invention has been completed. rice field. Accordingly, the present invention provides the following.
<1> A colored photosensitive resin composition containing a coloring material, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent,
The photopolymerization initiator contains a photopolymerization initiator a1 having an absorption coefficient of 8×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol,
The resin is a colored photosensitive resin composition containing a resin b1 containing a repeating unit b1-1 derived from a compound represented by the following formula (I) and a repeating unit b1-2 derived from an alkyl (meth)acrylate. ;

In the formula, X ¹ represents O or NH, R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, R ¹⁰ represents a substituent, m is an integer of 0 to 2 and p represents an integer of 1 or more.
<2> The colored photosensitive resin composition according to <1>, wherein the compound represented by formula (I) is a compound represented by the following formula (I-1);

In the formula, X ¹ represents O or NH, R ¹ represents a hydrogen atom or a methyl group, R ² , R ³ and R ¹¹ each independently represent a hydrocarbon group, and R ¹² represents a substituent. , n represents an integer of 0 to 15, m represents an integer of 0 to 2, p1 represents an integer of 0 or more, and q1 represents an integer of 1 or more.
<3> The colored photosensitive composition according to <1> or <2>, wherein the resin b1 contains 1 to 70 mol% of the repeating unit b1-1 and 1 to 70 mol% of the repeating unit b1-2 in the total repeating units. elastic resin composition.
<4> The colored photosensitive resin composition according to any one of <1> to <3>, wherein the resin further contains a resin b2 having an aromatic carboxyl group.
<5> The colored photosensitive resin composition according to <4>, wherein the resin b2 is a resin containing a repeating unit represented by the following formula (b2-1);

In the formula, Ar ¹ represents a group containing an aromatic carboxyl group, L ¹ represents --COO-- or --CONH--, and L ² represents a divalent linking group.
<6> The colored photosensitive resin composition according to any one of <1> to <5>, wherein the coloring material contains a pigment.
<7> The colored photosensitive resin composition according to <6>, wherein the pigment contains at least one selected from diketopyrrolopyrrole compounds and phthalocyanine compounds.
<8> The colored photosensitive resin composition according to any one of <1> to <7>, wherein the polymerizable monomer contains a polymerizable monomer having an acid group.
<9> The colored photosensitive resin composition according to any one of <1> to <8>, which is used for color filters.
<10> The colored photosensitive resin composition according to any one of <1> to <9>, which is for a solid-state imaging device.
<11> The colored photosensitive resin composition according to any one of <1> to <10>, which is used to form a colored layer in regions partitioned by partition walls.
<12> A film obtained from the colored photosensitive resin composition according to any one of <1> to <11>.
<13> A color filter obtained from the colored photosensitive resin composition according to any one of <1> to <11>.
<14> A step of forming a colored photosensitive resin composition layer on a support using the colored photosensitive resin composition according to any one of <1> to <11>; and forming a pattern on the composition layer.
<15> a support;
a partition provided on the support;
A structure having a colored layer obtained from the colored photosensitive resin composition according to any one of <1> to <11> provided on a support in a region partitioned by partition walls.
<16> A solid-state imaging device having the film according to <12>.
<17> An image display device comprising the film according to <12>.

According to the present invention, it is possible to provide a colored photosensitive resin composition capable of suppressing the occurrence of layer separation associated with exposure after exposure and forming a film having excellent moisture resistance. In addition, the present invention can provide a film, a color filter, a method for producing a color filter, a structure, a solid-state imaging device, and an image display device using the colored photosensitive resin composition.

1 is a side sectional view showing one embodiment of a structure of the present invention; FIG. It is the top view seen from just above the support body in the same structure.

The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "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).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, a pigment means a compound that is difficult to dissolve in a solvent.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .

<Colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention is a colored photosensitive resin composition containing a coloring material, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent,
The photopolymerization initiator contains a photopolymerization initiator a1 having an absorption coefficient of 8×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol,
The resin is characterized by containing a resin b1 containing a repeating unit b1-1 derived from a compound represented by formula (I) described below and a repeating unit b1-2 derived from an alkyl (meth)acrylate.

By containing the resin b1, the colored photosensitive resin composition of the present invention is excellent in moisture resistance and can form a film with suppressed film shrinkage even when exposed to a high-humidity environment. On the other hand, when the colored photosensitive resin composition using resin b1 was left after exposure, the exposed portion of the colored photosensitive resin composition tended to separate into layers, but the absorption of light at a wavelength of 365 nm in methanol. By using the photopolymerization initiator a1 having a coefficient of 8 × 10 ³ mL / gcm or more, even if the colored photosensitive resin composition after exposure is left for a long time, the layer in the exposed part of the colored photosensitive resin composition Separation can be suppressed. Therefore, according to the colored photosensitive resin composition of the present invention, it is possible to suppress the occurrence of layer separation due to the leaving after exposure and to form a film excellent in moisture resistance.

The colored photosensitive resin composition of the present invention can be preferably used as a colored photosensitive resin composition for color filters. Specifically, it can be preferably used as a colored photosensitive resin composition for forming pixels of a color filter. In addition, the colored photosensitive resin composition of the present invention can be preferably used as a colored photosensitive resin composition for solid-state imaging devices, and is a colored photosensitive resin composition for forming pixels of color filters used in solid-state imaging devices. It can be used more preferably as. In addition, the colored photosensitive resin composition of the present invention can also be preferably used as a colored photosensitive resin composition for display devices, and is more suitable as a colored photosensitive resin composition for forming pixels of color filters used in display devices. It can be preferably used. Moreover, it is preferable that the colored photosensitive resin composition of the present invention is used for forming a colored layer in a region partitioned by partition walls. The colored photosensitive resin composition of the present invention can also be used as a composition for forming color microlenses. Examples of a method for manufacturing a color microlens include the method described in Japanese Patent Application Laid-Open No. 2018-010162. The colored photosensitive resin composition of the present invention will be described in detail below.

<<coloring material>>
The colored photosensitive resin composition of the present invention contains a coloring material. Colorants include chromatic colorants such as red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. In the present invention, the coloring material may be a pigment or a dye. A pigment and a dye may be used in combination. Moreover, the pigment may be either an inorganic pigment or an organic pigment. As the pigment, an inorganic pigment or a material in which a part of an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.

The coloring material used in the present invention preferably contains a pigment. The content of the pigment in the coloring material is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. Especially preferred. Examples of pigments include those shown below.

Color Index (C.I.) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,231,232 etc. (above, yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, orange pigment),
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294, etc. , red pigment),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61, etc. (the above are purple pigments),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. , blue pigment).

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used. Specific examples include compounds described in International Publication WO2015/118720. Further, as a green pigment, a compound described in CN106909027A, a phthalocyanine compound having a phosphoric acid ester as a ligand, and the like can also be used.

Also, an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment. Specific examples include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

Further, as the yellow pigment, the pigment described in JP-A-2017-201003, the pigment described in JP-A-2017-197719, the paragraph numbers 0011-0062, 0137- of JP-A-2017-171912 0276, the pigments described in paragraph numbers 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, paragraph numbers 0011-0062 and 0139-0190 of JP-A-2017-171914 Pigments described in JP-A-2017-171915, paragraphs 0010 to 0065 and 0142 to 0222 can also be used.

Further, as a yellow pigment, the compound described in JP-A-2018-62644 can also be used. This compound can also be used as a pigment derivative.

As red pigments, diketopyrrolopyrrole-based pigments in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and diketopyrrolopyrrole-based pigments described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 Pigments and the like can also be used. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.

The pigment used in the present invention is also preferably at least one selected from diketopyrrolopyrrole compounds and phthalocyanine compounds. These compounds are likely to interact with resin b1 and the like, and therefore are likely to be firmly retained in the film, and are likely to form a film excellent in color resistance to developer and the like.

The pigment used in the present invention preferably contains a red pigment or a green pigment. As a red pigment, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264 and C.I. I. Pigment Red 272, C.I. I. Pigment Red 264 and C.I. I. Pigment Red 272 is preferred. As a green pigment, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62 and C.I. I. Pigment Green 63, C.I. I. Pigment Green 36, Pigment Green 59, C.I. I. Pigment Green 62 and C.I. I. Pigment Green 63 is preferred.

In the present invention, a dye can also be used as the coloring material. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used. Further, thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can also be preferably used. Further, as a yellow dye, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A-2013-54339, quinophthalone compounds described in paragraph numbers 0013-0058 of JP-A-2014-26228, JP-A-2018-12863 Intramolecular imide-type xanthene dyes described in publications can also be used.

In the present invention, a dye multimer can also be used as the coloring material. The dye multimer is preferably a dye that is dissolved in a solvent and used, but the dye multimer may form particles, and when the dye multimer is particles, it is usually dispersed in the solvent. Used. The particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682. A dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. A plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, and International Publication WO2016/031442. Compounds can also be used.

In the present invention, a pigment derivative can also be used as the coloring material. In the present invention, it is preferable to use a pigment and a pigment derivative together. Pigment derivatives include compounds having a structure in which a portion of the chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. Chromophores constituting pigment derivatives include quinoline skeletons, benzimidazolone skeletons, diketopyrrolopyrrole skeletons, azo skeletons, phthalocyanine skeletons, anthraquinone skeletons, quinacridone skeletons, dioxazine skeletons, and perinone skeletons. skeletons, perylene skeletons, thioindigo skeletons, isoindoline skeletons, isoindolinone skeletons, quinophthalone skeletons, threne skeletons, metal complex skeletons, quinoline skeletons, benzimidazolone skeletons, diketo Pyrrolopyrrole-based skeletons, azo-based skeletons, quinophthalone-based skeletons, isoindoline-based skeletons and phthalocyanine-based skeletons are preferred, and azo-based skeletons and benzimidazolone-based skeletons are more preferred. The acid group possessed by the pigment derivative is preferably a sulfo group or a carboxyl group, more preferably a sulfo group. The basic group possessed by the pigment derivative is preferably an amino group, more preferably a tertiary amino group. Specific examples of the pigment derivative include the compounds described in Examples below and the compounds described in paragraphs 0162 to 0183 of JP-A-2011-252065. The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

The content of the coloring material is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more, based on the total solid content of the colored photosensitive resin composition. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less.

In the colored photosensitive resin composition of the present invention, the total content of the pigment is preferably 20% by mass or more, more preferably 25% by mass or more, based on the total solid content of the colored photosensitive resin composition, and 30% by mass. % or more is more preferable. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less. Further, in the colored photosensitive resin composition of the present invention, the total content of the pigment and the pigment derivative is preferably 20% by mass or more, more preferably 25% by mass or more, based on the total solid content of the colored photosensitive resin composition. is more preferable, and 30% by mass or more is even more preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less.

<<Resin>>
The colored photosensitive resin composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the purpose of binder. A resin mainly used for dispersing particles and the like in a composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

(Resin b1)
The colored photosensitive resin composition of the present invention contains a resin b1 containing a repeating unit b1-1 derived from the compound represented by formula (I) and a repeating unit b1-2 derived from an alkyl (meth)acrylate. . Since the colored photosensitive resin composition of the present invention contains the resin b1, it can form a film having excellent moisture resistance.

The weight average molecular weight of resin b1 is preferably 3,000 to 70,000. The upper limit is preferably 60,000 or less, more preferably 50,000 or less, even more preferably 40,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more, and even more preferably 6,000 or more. If the weight-average molecular weight of the resin b1 is within the above range, the above effects can be obtained more remarkably.

Resin b1 preferably contains 1 to 70 mol % of repeating unit b1-1 and 1 to 70 mol % of repeating unit b1-2 in all repeating units.

The content of repeating unit b1-1 in all repeating units of resin b1 is preferably 3 to 40 mol %. The lower limit is preferably 4 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 35 mol % or less, more preferably 30 mol % or less. If the content of the repeating unit b1-1 is within the above range, the above effects can be obtained more remarkably.

The content of repeating units b1-2 in all repeating units of resin b1 is preferably 5 to 60 mol %. The lower limit is preferably 8 mol % or more, more preferably 10 mol % or more. The upper limit is preferably 50 mol % or less, more preferably 45 mol % or less. If the content of the repeating unit b1-2 is within the above range, the above effects can be obtained more remarkably.

The total content of repeating unit b1-1 and repeating unit b1-2 in all repeating units of resin b1 is preferably 5 mol% or more, more preferably 10 mol% or more, and 20 mol. % or more is more preferable. The upper limit can be 100 mol %, 80 mol % or less, or 60 mol % or less.

The ratio of the number of moles of repeating unit b1-1 to the number of moles of repeating unit b1-2 in all repeating units of resin b1 is the number of moles of repeating unit b1-1: the number of moles of repeating unit b1-2=1: It is preferably 0.3 to 7, more preferably 1:0.4 to 6, even more preferably 1:0.5 to 5.

[Repeating unit b1-1]
First, the repeating unit b1-1 of the resin b1 will be described. The repeating unit b1-1 is a repeating unit derived from the compound represented by formula (I).

In formula (I), X ¹ represents O or NH, preferably O.
In formula (I), R ¹ represents a hydrogen atom or a methyl group.
In formula (I), L ¹ represents a divalent linking group. Divalent linking groups include hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S- and these A group formed by combining two or more of Examples of hydrocarbon groups include alkyl groups and aryl groups. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered ring. Types of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of heteroatoms constituting the heterocyclic group is preferably 1-3. The heterocyclic group may be monocyclic or condensed. A hydrocarbon group and a heterocyclic group may have a substituent. Examples of substituents include alkyl groups, aryl groups, hydroxy groups, and halogen atoms.
In formula (I), R ¹⁰ represents a substituent. Examples of the substituent represented by R ¹⁰ include the substituent T shown below, preferably a hydrocarbon group, more preferably an alkyl group optionally having an aryl group as a substituent.
In formula (I), m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0. In addition, p represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1.

(substituent T)
The substituent T includes a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , - CONRt ¹ Rt ² , —NHCONRt ¹ Rt ² , —NHCOORt ¹ , —SRt ¹ , —SO ₂ Rt ¹ , —SO ₂ ORt ¹ , —NHSO ₂ Rt ¹ or —SO ₂ NRt ¹ Rt ² . Rt ¹ and Rt ² each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rt ¹ and Rt ² may combine to form a ring.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-15, even more preferably 1-8. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably branched.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched.
The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, preferably linear or branched.
The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12.
The heterocyclic group may be monocyclic or condensed. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3. A heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12.
A hydrocarbon group and a heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the substituent T described above.

The compound represented by formula (I) is preferably a compound represented by formula (I-1) below.

In formula (I-1), X ¹ represents O or NH, preferably O.
In formula (I-1), R ¹ represents a hydrogen atom or a methyl group.
In formula (I-1), R ² , R ³ and R ¹¹ each independently represent a hydrocarbon group. The hydrocarbon group represented by R ² and R ³ is preferably an alkylene group or an arylene group, more preferably an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. The hydrocarbon group represented by R ³ is preferably an alkyl group optionally having an aryl group as a substituent, more preferably an alkyl group having an aryl group as a substituent. The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-10, even more preferably 1-5. When the alkyl group has an aryl group as a substituent, the number of carbon atoms in the alkyl group means the number of carbon atoms in the alkyl moiety.
In formula (I-1), R ¹² represents a substituent. Examples of the substituent represented by R ¹² include the substituent T described above.
In formula (I-1), n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and an integer of 0 to 3. More preferred. Further, m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0. Further, p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, even more preferably 0 to 1, and particularly preferably 0. Also, q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1.

The compound represented by Formula (I) is preferably a compound represented by Formula (III) below.

In formula (III), R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0-15. The number of carbon atoms in the alkylene group represented by R ²¹ and R ²² is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.

Examples of the compound represented by formula (I) include ethylene oxide- or propylene oxide-modified (meth)acrylates of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

[Repeating unit b1-2]
Next, the repeating unit b1-2 of the resin b1 will be described. Repeating unit b1-2 is a repeating unit derived from alkyl (meth)acrylate. The number of carbon atoms in the alkyl moiety of the alkyl (meth)acrylate is preferably 3-10, more preferably 3-8, even more preferably 3-6. Preferred specific examples of alkyl (meth)acrylates include n-butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate. ) is preferably an acrylate.

[Repeating unit b1-3]
Resin b1 preferably further contains a repeating unit having an acid group (hereinafter also referred to as repeating unit b1-3). According to this aspect, it is possible to obtain a colored photosensitive resin composition having excellent pattern formability in a photolithographic method. The acid group includes a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and is preferably a carboxyl group.

When the resin b1 contains the repeating unit b1-3, the content of the repeating unit b1-3 in the total repeating units of the resin b1 is preferably 1 to 60 mol %. The lower limit is preferably 5 mol % or more, more preferably 10 mol % or more. The upper limit is preferably 50 mol % or less, more preferably 40 mol % or less.

Further, when the resin b1 contains the repeating unit b1-3, the acid value of the resin b1 is preferably 20 to 300 mgKOH/g from the viewpoint of pattern formability. The lower limit is more preferably 60 mgKOH/g or more, still more preferably 80 mgKOH/g or more. The upper limit is more preferably 280 mgKOH/g or less, still more preferably 250 mgKOH/g or less.

[Other repeating units]
The resin b1 can contain repeating units other than the repeating units b1-1 to b1-3 described above (hereinafter also referred to as other repeating units). Other repeating units include repeating units having a polymerizable group. When the resin b1 contains a repeating unit having a polymerizable group, it is possible to form a film with heat resistance and suppressed color loss during development. Polymerizable groups include ethylenically unsaturated groups such as vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. When the resin b1 contains the repeating unit b1-4, the content of the repeating unit b1-4 in the total repeating units of the resin b1 is preferably 1 to 60 mol %. The lower limit is preferably 5 mol % or more, more preferably 10 mol % or more. The upper limit is preferably 50 mol % or less, more preferably 40 mol % or less.

(Resin b2)
The colored photosensitive resin composition of the present invention preferably further contains a resin b2 having an aromatic carboxyl group in addition to the resin b1. According to this aspect, since the repeating unit b1-1 of the resin b1 and the aromatic carboxyl group of the resin b2 contain similar structures, the interaction between the resin b1 and the resin b2 is strong, and the pigment b1 and the coloring material, and also between the pigment b2 and the coloring material. It is also possible to form a film excellent in color fastness.

In resin b2, the aromatic carboxyl group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. It is preferable that the aromatic carboxyl group is contained in the main chain of the repeating unit because the above-mentioned effects are likely to be obtained more remarkably. Although the details are unknown, it is presumed that these properties are further improved by the presence of aromatic carboxyl groups near the main chain. In this specification, an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In the aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.

式（ｂ２－１）中、Ａｒ^１は芳香族カルボキシル基を含む基を表し、Ｌ^１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ^２は、２価の連結基を表す。
式（ｂ２－１０）中、Ａｒ^１０は芳香族カルボキシル基を含む基を表し、Ｌ^１１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ^１２は３価の連結基を表し、Ｐ^１０はポリマー鎖を表す。 Resin b2 is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (b2-1) and repeating units represented by formula (b2-10).

In formula (b2-1), Ar ¹ represents a group containing an aromatic carboxyl group, L ¹ represents -COO- or -CONH-, and L ² represents a divalent linking group.
In formula (b2-10), Ar ¹⁰ represents a group containing an aromatic carboxyl group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, and P ¹⁰ represents a polymer represents a chain.

First, the formula (b2-1) will be explained. Examples of the aromatic carboxyl group-containing group represented by Ar ¹ in formula (b2-1) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like. Aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds having the following structures.

In the above formula, Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

Specific examples of the aromatic tricarboxylic anhydride include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.) , Naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalene tricarboxylic anhydride, etc.), 3,4,4′-benzophenonetricarboxylic anhydride, 3,4,4′-biphenyl ether tricarboxylic anhydride, 3,4,4′-biphenyltricarboxylic anhydride, 2,3 ,2′-biphenyltricarboxylic anhydride, 3,4,4′-biphenylmethanetricarboxylic anhydride, or 3,4,4′-biphenylsulfonetricarboxylic anhydride. Specific examples of aromatic tetracarboxylic acid anhydrides include pyromellitic anhydride, ethylene glycol dianhydride trimellitic ester, propylene glycol dianhydride trimellitic ester, butylene glycol dianhydride trimellitic ester, and 3,3′. ,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2 ,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3′,4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis(3,4 -dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane di anhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3, 4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, or 3,4-dicarboxy-1,2 , 3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride and the like.

Specific examples of the group containing an aromatic carboxyl group represented by Ar ¹ include a group represented by formula (Ar-1), a group represented by formula (Ar-2), and a group represented by formula (Ar-3). and the like.

In formula (Ar-1), n1 represents an integer of 1 to 4, preferably an integer of 1 to 2, more preferably 2.
In formula (Ar-2), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 to 2, even more preferably 2.
In formula (Ar-3), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 to 2, preferably 1 More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In formula (Ar-3), Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, the above formula (Q- 1) or a group represented by the above formula (Q-2).

In formula (b2-1), L ¹ represents -COO- or -CONH-, preferably -COO-.

The divalent linking group represented by L ² in formula (b2-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these A group obtained by combining two or more of The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The alkylene group may be linear, branched or cyclic. The arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The divalent linking group represented by L ² is preferably a group represented by -OL ^2a -O-. L ^2a is an alkylene group; an arylene group; a combination of an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group; Groups in which at least one selected from -NH- and -S- are combined. The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The alkylene group may be linear, branched or cyclic. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent.

Next, the formula (b2-10) will be explained. The group containing an aromatic carboxyl group represented by Ar ¹⁰ in formula (b2-10) has the same meaning as Ar ¹ in formula (b2-1), and the preferred range is also the same.

In formula (b2-10), L ¹¹ represents -COO- or -CONH-, preferably -COO-.

The trivalent linking group represented by L ¹² in formula (b2-10) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10. The hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1) below, more preferably a group represented by formula (L12-2).

L ^12a and L ^12b each represent a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (b2-10), *2 represents formula (b2-10) represents the binding position with ^P10 .

The trivalent linking group represented by L ^12a and L ^12b is selected from a hydrocarbon group; a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH- and -S- Groups in which at least one of them is combined, and the like.

In formula ( ^b2-10 ), P10 represents a polymer chain. The polymer chain represented by ^P10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units. The weight average molecular weight of the polymer chain P10 is preferably ^500-20,000 . The lower limit is preferably 500 or more, more preferably 1000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of ^P10 is within the above range, the dispersibility of the pigment in the composition is good. When resin b2 is a resin having a repeating unit represented by formula (b2-10), resin b2 is preferably used as a dispersant.

上記式において、Ｒ^Ｐ１およびＲ^Ｐ２は、それぞれアルキレン基を表す。Ｒ^Ｐ１およびＲ^Ｐ２で表されるアルキレン基としては、炭素数１～２０の直鎖状又は分岐状のアルキレン基が好ましく、炭素数２～１６の直鎖状又は分岐状のアルキレン基がより好ましく、炭素数３～１２の直鎖状又は分岐状のアルキレン基が更に好ましい。
上記式において、Ｒ^Ｐ３は、水素原子またはメチル基を表す。
上記式において、Ｌ^Ｐ１は、単結合またはアリーレン基を表し、Ｌ^Ｐ２は、単結合または２価の連結基を表す。Ｌ^Ｐ１は、単結合であることが好ましい。Ｌ^Ｐ２が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ_２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－、－ＮＨＣＯ－、－ＣＯＮＨ－、およびこれらの２以上を組み合わせてなる基が挙げられる。
Ｒ^Ｐ４は、水素原子または置換基を表す。置換基としては、ヒドロキシ基、カルボキシル基、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、（メタ）アクリロイル基、オキセタニル基、ブロックイソシアネート基等が挙げられる。なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。ブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。ブロック剤については、特開２０１７－０６７９３０号公報の段落番号０１１５～０１１７に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、ブロックイソシアネート基は、９０～２６０℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。 In formula (b2-10), the polymer chain represented by P10 is preferably a polymer chain containing repeating units represented by the following formulas (P ^- 1) to (P-5), and (P-5) More preferably, it is a polymer chain containing a repeating unit represented by.

In the above formula, R ^P1 and R ^P2 each represent an alkylene group. The alkylene group represented by R ^P1 and R ^P2 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms. , a linear or branched alkylene group having 3 to 12 carbon atoms is more preferable.
In the above formula, R ^P3 represents a hydrogen atom or a methyl group.
In the above formula, ^LP1 represents a single bond or an arylene group, and ^LP2 represents a single bond or a divalent linking group. L ^P1 is preferably a single bond. The divalent linking group represented by L ^P2 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), —NH—, —SO—, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO-, -CONH-, and groups consisting of combinations of two or more of these.
R ^P4 represents a hydrogen atom or a substituent. Substituents include hydroxy group, carboxyl group, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, (meth)acryloyl groups, oxetanyl groups, blocked isocyanate groups, and the like. The blocked isocyanate group in the present invention is a group capable of generating an isocyanate group by heat. For example, a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified. Examples of blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. Blocking agents include compounds described in paragraphs 0115 to 0117 of JP-A-2017-067930, the contents of which are incorporated herein. Also, the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heating at 90 to 260°C.

The polymer chain represented by ^P10 preferably has at least one group (hereinafter also referred to as functional group A) selected from a (meth)acryloyl group, an oxetanyl group, a blocked isocyanate group and a t-butyl group. Functional group A is more preferably at least one selected from (meth)acryloyl groups, oxetanyl groups and blocked isocyanate groups. When the polymer chain contains the functional group A, it is easy to form a film having excellent solvent resistance. In particular, when at least one group selected from a (meth)acryloyl group, an oxetanyl group and a blocked isocyanate group is included, the above effects are remarkable. Moreover, when the functional group A has a t-butyl group, it is preferable that the composition contains a compound having an epoxy group or an oxetanyl group. When the functional group A has a blocked isocyanate group, the composition preferably contains a compound having a hydroxyl group.

Moreover, the polymer chain represented by ^P10 is more preferably a polymer chain having a repeating unit containing the functional group A in the side chain. In addition, the proportion of repeating units containing the functional group A in the side chain in all repeating units constituting P10 is preferably 5% by mass or more, more preferably ¹⁰ % by mass or more, and 20% by mass or more. % by mass or more is more preferable. The upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.

Also, the polymer chain represented by ^P10 preferably has a repeating unit containing an acid group. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. According to this aspect, the dispersibility of the pigment in the composition can be further improved. Furthermore, the developability can be further improved. The proportion of repeating units containing an acid group is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, even more preferably 3 to 10% by mass.

Resin b2 can be produced by reacting at least one acid anhydride selected from aromatic tetracarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides with a hydroxyl group-containing compound. Examples of the aromatic tetracarboxylic anhydride and the aromatic tricarboxylic anhydride include those described above. The hydroxyl group-containing compound is not particularly limited as long as it has a hydroxyl group in its molecule, but it is preferably a polyol having two or more hydroxyl groups in its molecule. It is also preferable to use a compound having two hydroxyl groups and one thiol group in the molecule as the hydroxyl group-containing compound. Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1,2-propane. Diol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto -2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like. Other hydroxyl group-containing compounds include compounds described in paragraphs 0084 to 0095 of JP-A-2018-101039, the contents of which are incorporated herein.

The molar ratio of the acid anhydride group in the acid anhydride to the hydroxyl group in the hydroxyl group-containing compound (acid anhydride group/hydroxyl group) is preferably 0.5 to 1.5.

Further, the resin containing the repeating unit represented by the above formula (b2-10) can be synthesized by the following synthesis methods (1) and (2).

[Synthesis method (1)]
A polymerizable monomer having an ethylenically unsaturated group is radically polymerized in the presence of a hydroxyl group-containing thiol compound (preferably a compound having two hydroxyl groups and one thiol group in the molecule) to form two hydroxyl groups in one terminal region. and reacting the synthesized vinyl polymer with one or more aromatic acid anhydrides selected from aromatic tetracarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides. .

[Synthesis method (2)]
A hydroxyl group-containing compound (preferably a compound having two hydroxyl groups and one thiol group in the molecule), one or more aromatic acid anhydrides selected from aromatic tetracarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides, and then radically polymerizing a polymerizable monomer having an ethylenically unsaturated group in the presence of the resulting reactant. In the synthesis method (2), after radically polymerizing a polymerizable monomer having a hydroxyl group, a compound having an isocyanate group (for example, a compound having an isocyanate group and the functional group A described above) may be reacted. This makes it possible to introduce the functional group A into the polymer chain ^P10 .

Resin b2 can also be synthesized according to the method described in paragraphs 0120 to 0138 of JP-A-2018-101039.

The weight average molecular weight of resin b2 is preferably 2,000 to 35,000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less. The lower limit is preferably 4,000 or more, more preferably 6,000 or more, and even more preferably 7,000 or more. When the weight-average molecular weight of the resin b2 is within the above range, the above effects can be obtained more significantly. Moreover, the storage stability of the colored photosensitive resin composition can also be improved.

The acid value of resin b2 is preferably 5 to 200 mgKOH/g. The upper limit is preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, and even more preferably 80 mgKOH/g or less. The lower limit is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and even more preferably 20 mgKOH/g or more. If the acid value of the resin b2 is within the above range, the above effects can be obtained more remarkably. In addition, a suitable pigment adsorption capacity can be obtained, and pigment dispersibility in the composition can be enhanced. Furthermore, the storage stability of the colored photosensitive resin composition can also be improved.

(other resin)
The colored photosensitive resin composition of the present invention can further contain resins other than the resins b1 and b2 (hereinafter also referred to as other resins).

The weight average molecular weight (Mw) of other resins is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

Other resins include, for example, (meth)acrylic resins, (meth)acrylamide resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, Examples include polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins.

Another resin is preferably a resin having an acid group. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. A resin having an acid group can also be used as an alkali-soluble resin or a dispersant. The acid value of the resin having acid groups is preferably 20-300 mgKOH/g. The lower limit is more preferably 60 mgKOH/g or more, still more preferably 80 mgKOH/g or more. The upper limit is more preferably 280 mgKOH/g or less, still more preferably 250 mgKOH/g or less.

Other resins include repeating units derived from compounds represented by the following formula (ED1) and/or compounds represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that the resin contains

式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In formula (ED1), 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.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.

Specific examples of the ether dimer can be referred to paragraph number 0317 of JP-A-2013-29760, the content of which is incorporated herein.

Another resin is preferably a resin containing a repeating unit having a polymerizable group. By using a resin containing a repeating unit having a polymerizable group, it is possible to form a film excellent in color removal resistance, solvent resistance and heat resistance. Polymerizable groups include ethylenically unsaturated groups such as vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

Another resin is preferably a resin containing a repeating unit having a maleimide structure. In addition, in this specification, the maleimide structure means a structure derived from a maleimide compound. Maleimide compounds include maleimides and N-substituted maleimides. N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide and the like. The maleimide structure may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The maleimide structure is preferably contained in the main chain of the repeating unit because it facilitates the formation of a film with excellent developability and color removal performance.

The colored photosensitive resin composition of the present invention can contain a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol% is preferable. A resin consisting only of acid groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, it is possible to further suppress the generation of development residues when forming a pattern by photolithography.

It is also preferable that the resin used as the dispersant is a graft resin. Details of the graft resin can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

It is also preferable that the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. A resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion. Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated group on its side chain. The content of repeating units having an ethylenically unsaturated group in a side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70 mol% of the total repeating units of the resin. is more preferable.

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by BYK Chemie (e.g., Disperbyk-111, 2001, etc.), Solsperse series manufactured by Nippon Lubrizol Co., Ltd. ( For example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine-Techno Co., Inc., and the like can be mentioned. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.

The resin content in the total solid content of the colored photosensitive resin composition of the present invention is preferably 10 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more.

The content of the resin b1 in the total solid content of the colored photosensitive resin composition is preferably 3 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 4% by mass or more, more preferably 5% by mass or more.

The content of the resin b1 in the resin contained in the colored photosensitive resin composition is preferably 5 to 100% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.

When the colored photosensitive resin composition of the present invention contains the resin b2, the content of the resin b2 in the resin contained in the colored photosensitive resin composition is preferably 1 to 95% by mass. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more. The content of resin b2 is preferably 10 to 95 parts by mass with respect to 100 parts by mass of resin b1. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. The upper limit is preferably 90 parts by mass or less, more preferably 85 parts by mass or less. Further, the total content of the resin b1 and the resin b2 in the total solid content of the colored photosensitive resin composition is preferably 10 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more.

When the colored photosensitive resin composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less. The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
Also, the content of the resin as a dispersant is preferably 5 to 150 parts by mass with respect to the total of 100 parts by mass of the pigment and the pigment derivative. The upper limit is preferably 120 parts by mass or less, more preferably 100 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more.
Further, when the resin b2 is used as a dispersant, the content of the resin b2 in the total amount of the dispersant is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and 50 to 100% by mass. % by mass is more preferred.

<<polymerizable monomer>>
The colored photosensitive resin composition of the present invention contains a polymerizable monomer. Examples of polymerizable monomers include compounds having an ethylenically unsaturated group. Examples of ethylenically unsaturated groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. The polymerizable monomer is preferably a radically polymerizable compound (radical polymerizable monomer).

The molecular weight of the polymerizable monomer is preferably 100-2000. The upper limit is preferably 1500 or less, more preferably 1000 or less. The lower limit is more preferably 150 or more, even more preferably 250 or more.

The ethylenically unsaturated group value (hereinafter referred to as C=C value) of the polymerizable monomer is preferably 2 to 14 mmol/g from the viewpoint of the stability of the composition over time. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more. The upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less. The C=C value of the polymerizable monomer was calculated by dividing the number of ethylenically unsaturated groups contained in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

The polymerizable monomer is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 4 or more ethylenically unsaturated groups. According to this aspect, the curability of the colored photosensitive resin composition by exposure is good. From the viewpoint of the stability of the composition over time, the upper limit of the ethylenically unsaturated groups is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. Further, the polymerizable monomer is preferably a trifunctional or higher (meth)acrylate compound, more preferably a tri- to fifteen-functional (meth)acrylate compound, and a tri- to ten-functional (meth)acrylate compound. is more preferred, and tri- to hexa-functional (meth)acrylate compounds are particularly preferred.

The polymerizable monomer used in the present invention is preferably a compound having a molecular weight of 450 or less containing 3 or more ethylenically unsaturated groups, more preferably a compound having a molecular weight of 450 or less containing 3 ethylenically unsaturated groups. A trifunctional (meth)acrylate compound having a molecular weight of 450 or less is preferred, and more preferred. According to this aspect, the solvent resistance of the resulting film can be further improved. Examples of the polymerizable monomer having a molecular weight of 450 or less and containing three ethylenically unsaturated groups include trimethylolpropane triacrylate, tris(2-acryloyloxyethyl) isocyanurate, and trimethylolpropane ethylene-modified triacrylate.

The polymerizable monomer used in the invention is also preferably a compound having an isocyanurate skeleton. By using a polymerizable monomer having an isocyanurate skeleton, the solvent resistance of the resulting film can be improved. Specific examples of polymerizable monomers having an isocyanurate skeleton include tris(2-acryloyloxyethyl) isocyanurate and ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate. Commercially available products include Fancryl FA-731A (manufactured by Hitachi Chemical Co., Ltd.), NK Ester A9300, A9300-1CL, A9300-3CL (manufactured by Shin-Nakamura Chemical Co., Ltd., Aronix M-315 (Toagosei Co., Ltd. ) made) and the like.

In the present invention, as the polymerizable monomer, dipentaerythritol triacrylate (as a commercial product KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product KAYARAD D-320; Nippon Kayaku Yaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer) can also be used. Further, as polymerizable monomers, Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate), NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., penta Erythritol tetraacrylate) can also be used.

In the present invention, it is preferable to use a polymerizable monomer having an acid group as the polymerizable monomer. By using a polymerizable monomer having an acid group, the colored photosensitive resin composition layer in the unexposed area can be easily removed during development, and generation of development residue can be suppressed. The acid group includes a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferred. Examples of the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta(meth)acrylate. Commercially available polymerizable monomers having an acid group include Aronix M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The acid value of the polymerizable monomer having an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. When the acid value of the polymerizable monomer is 0.1 mgKOH/g or more, the solubility in the developing solution is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling.

In the present invention, it is also preferable to use a compound having a caprolactone structure as the polymerizable monomer. Polymerizable monomers having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60 and DPCA-120.

Polymerizable monomers, JP 2017-48367, JP 6057891, compounds described in JP 6031807, compounds described in JP 2017-194662, 8UH-1006, 8UH -1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are also preferably used.

The content of the polymerizable monomer is preferably 2 to 30% by mass based on the total solid content of the colored photosensitive resin composition. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The number of polymerizable monomers contained in the colored photosensitive resin composition may be one, or two or more. When two or more types are used, the total amount thereof is preferably within the above range.

Further, the total content of the resin and the polymerizable monomer in the total solid content of the colored photosensitive resin composition is preferably 10 to 50% by mass. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

Also, the content of the polymerizable monomer is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the resin. The upper limit is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more.

Also, the content of the polymerizable monomer is preferably 10 to 2000 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. The upper limit is preferably 1800 parts by mass or less, more preferably 1500 parts by mass or less. The lower limit is preferably 30 parts by mass or more, more preferably 50 parts by mass or more.

<<Photoinitiator>>
The colored photosensitive resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, and oxime derivatives. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoacetophenone compounds, hydroxyacetophenone compounds, phenylglyoxylate compounds and the like. Specific examples of the photopolymerization initiator can be referred to, for example, paragraphs 0265 to 0268 of JP-A-2013-29760, the contents of which are incorporated herein.

Commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF). Commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162) compound described in, Journal of Photopolymer Science and Technology (1995, pp.202-232) compound described in JP-A-2000-66385, Compounds described in JP-A-2000-80068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-19766, Patent No. 6065596, the compound described in WO2015/152153, the compound described in WO2017/051680, the compound described in JP 2017-198865, WO2017/164127 Examples thereof include compounds described in paragraph numbers 0025 to 0038 of the publication. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), and Adeka Optomer N-1919. (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-14052). As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

The oxime compound is preferably an oxime compound having a fluorine atom. The oxime compound containing a fluorine atom preferably has a group containing a fluorine atom. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing group). The fluorine-containing group includes -OR ^F1 , -SR ^F1 , -COR ^F1 , -COOR ^F1 , -OCOR ^F1 , -NR ^F1 R ^F2 , -NHCOR ^F1 , -CONR ^F1 R ^F2 , -NHCONR ^F1 R ^F2 , -NHCOOR At least one group selected from ^F1 , —SO ₂ R ^F1 , —SO ₂ OR ^F1 and —NHSO ₂ R ^F1 is preferred. R ^F1 represents a fluorine-containing alkyl group, and R ^F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group, or a heterocyclic group. The fluorine-containing group is preferably -OR ^F1 .

The number of carbon atoms in the alkyl group and fluorine-containing alkyl group is preferably 1-20, more preferably 1-15, still more preferably 1-10, and particularly preferably 1-4. Alkyl groups and fluorine-containing alkyl groups may be linear, branched, or cyclic, but are preferably linear or branched. In the fluorine-containing alkyl group, the fluorine atom substitution rate is preferably 40 to 100%, more preferably 50 to 100%, even more preferably 60 to 100%. The substitution ratio of fluorine atoms refers to the ratio (%) of the number of fluorine atoms substituted with respect to the total number of hydrogen atoms in an alkyl group.

The number of carbon atoms in the aryl group is preferably 6-20, more preferably 6-15, even more preferably 6-10.

The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic group may be monocyclic or condensed. The condensation number is preferably 2-8, more preferably 2-6, even more preferably 3-5, and particularly preferably 3-4. The number of carbon atoms constituting the heterocyclic group is preferably 3-40, more preferably 3-30, even more preferably 3-20. The number of heteroatoms constituting the heterocyclic group is preferably 1-3. The heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom.

The group containing a fluorine atom preferably has a terminal structure represented by formula (1) or (2). * in the formula represents a link.
*—CHF ₂ (1)
*-CF ₃ (2)

The total number of fluorine atoms in the oxime compound containing fluorine atoms is preferably 3 or more, more preferably 4-10.

式（ＯＸ－１）において、Ａｒ^Ｘ１およびＡｒ^Ｘ２は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表し、Ｒ^Ｘ１は、フッ素原子を含む基を有するアリール基を表し、Ｒ^Ｘ２およびＲ^Ｘ３は、それぞれ独立に、アルキル基またはアリール基を表す。 The oxime compound containing a fluorine atom is preferably a compound represented by formula (OX-1).
(OX-1)

In formula (OX-1), Ar 1 ^X1 and Ar ^{2 X2} each independently represent an optionally substituted aromatic hydrocarbon ring, and R 1 ^X1 represents an aryl group having a fluorine atom-containing group. and R ^X2 and R ^X3 each independently represent an alkyl group or an aryl group.

Ar ^X1 and Ar ^X2 each independently represent an aromatic hydrocarbon ring which may have a substituent. The aromatic hydrocarbon ring may be monocyclic or condensed. The number of carbon atoms constituting the aromatic hydrocarbon ring is preferably 6-20, more preferably 6-15, and particularly preferably 6-10. Aromatic hydrocarbon rings are preferably benzene rings and naphthalene rings. Among them, at least one of Ar 1 ^X1 and Ar ^{2 X2} is preferably a benzene ring, and more preferably Ar ^{1 X1} is a benzene ring. Ar ^X2 is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

Examples of substituents that Ar ^X1 and Ar ^X2 may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR ^X11 , —SR ^X11 , —COR ^X11 , and —COOR ^X11 . , -OCOR ^X11 , -NR ^X11 R ^X12 , -NHCOR ^X11 , -CONR ^X11 R ^X12 , -NHCONR ^X11 R ^X12 , -NHCOOR ^X11 , -SO ₂ R ^X11 , -SO ₂ OR ^X11 , -NHSO ₂ R ^X11 , etc. mentioned. R ^X11 and R ^X12 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The alkyl group as a substituent and the alkyl group represented by R 1 ^X11 and R 1 ^X12 preferably have 1 to 30 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. Some or all of the hydrogen atoms in the alkyl group may be substituted with halogen atoms (preferably fluorine atoms). Also, some or all of the hydrogen atoms in the alkyl group may be substituted with the above substituents. The aryl group as a substituent and the aryl group represented by R 1 ^X11 and R 1 ^X12 preferably have 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aryl group may be monocyclic or condensed. Also, some or all of the hydrogen atoms in the aryl group may be substituted with the above substituents. The heterocyclic group as a substituent and the heterocyclic group represented by R ¹¹ and R ¹² are preferably 5- or 6-membered rings. The heterocyclic group may be monocyclic or condensed. The number of carbon atoms constituting the heterocyclic group is preferably 3-30, more preferably 3-18, even more preferably 3-12. The number of heteroatoms constituting the heterocyclic group is preferably 1-3. A heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In addition, some or all of the hydrogen atoms in the heterocyclic group may be substituted with the above substituents.

The aromatic hydrocarbon ring represented by Ar ^{1 X1} is preferably unsubstituted. The aromatic hydrocarbon ring represented by Ar ^{2 X2} may be unsubstituted or may have a substituent. It preferably has a substituent. As a substituent, -COR ^X11 is preferred. R ^X11 is preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an aryl group. The aryl group may have a substituent or may be unsubstituted. Examples of substituents include alkyl groups having 1 to 10 carbon atoms.

R ^X1 represents an aryl group having a fluorine atom-containing group. The number of carbon atoms in the aryl group is preferably 6-20, more preferably 6-15, even more preferably 6-10. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (fluorine-containing group). The fluorine atom-containing group is synonymous with the range described above, and the preferred range is also the same.

R ^X2 represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group and aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the above-mentioned substituents that Ar 1 ^X1 and Ar ² may have. The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-15, even more preferably 1-10, and particularly preferably 1-4. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. The number of carbon atoms in the aryl group is preferably 6-20, more preferably 6-15, even more preferably 6-10.

R ^X3 represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group and aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the above-mentioned substituents that Ar 1 ^X1 and Ar ² may have. The number of carbon atoms in the alkyl group represented by R 1 ^X3 is preferably 1-20, more preferably 1-15, even more preferably 1-10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. The number of carbon atoms in the aryl group represented by R 1 ^X3 is preferably 6-20, more preferably 6-15, even more preferably 6-10.

Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.

Moreover, the oxime compound can also use the oxime compound which has a fluorene ring. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A-2014-137466. The contents of which are incorporated herein.

An oxime compound having a benzofuran skeleton can also be used as the oxime compound. Specific examples include compounds OE-01 to OE-75 described in International Publication WO2015/036910.

Moreover, the oxime compound can also use an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication WO2013/083505.

Moreover, the oxime compound can use the oxime compound which has a nitro group. The oxime compound having a nitro group is also preferably a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249, paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466, and Japanese Patent No. 4223071. Compounds described in paragraphs 0007 to 0025 of the publication, ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.), and the like.

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

In the present invention, a bifunctional or trifunctional or higher photopolymerization initiator may be used as the photopolymerization initiator. Specific examples of bifunctional or trifunctional or higher photopolymerization initiators include JP-A-2010-527339, JP-A-2011-524436, International Publication WO2015/004565, and paragraphs of JP-A-2016-532675. Nos. 0417-0412, dimers of oxime compounds described in paragraphs 0039-0055 of International Publication WO2017/033680, compounds (E) and compounds (G ), Cmpd1 to 7 described in International Publication WO2016/034963, an oxime ester photoinitiator described in paragraph number 0007 of JP 2017-523465, paragraph of JP 2017-167399 Photoinitiators described in numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, and the like.

In the present invention, a photopolymerization initiator a1 (hereinafter also referred to as photopolymerization initiator a1) having an absorption coefficient of 8×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol is used as the photopolymerization initiator. As the photopolymerization initiator a1, a compound having the absorption coefficient described above can be selected and used from the compounds described above.

上記式においてεは吸光係数（ｍＬ／ｇｃｍ）、Ａは吸光度、ｃは光重合開始剤の濃度（ｇ／ｍＬ）、ｌは光路長（ｃｍ）を表す。 In the present invention, the absorption coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, it was calculated by dissolving a photopolymerization initiator in methanol to prepare a measurement solution and measuring the absorbance of the above-mentioned measurement solution. Specifically, the measurement solution described above is placed in a glass cell with a width of 1 cm, and the absorbance is measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent Technologies. The extinction coefficient (mL/gcm) at 254 nm was calculated.

In the above formula, ε is the extinction coefficient (mL/gcm), A is the absorbance, c is the concentration of the photopolymerization initiator (g/mL), and l is the optical path length (cm).

The absorption coefficient of light with a wavelength of 365 nm in methanol of the photopolymerization initiator a1 is preferably 1.0×10 ⁴ mL/gcm or more, more preferably 1.1×10 ⁴ mL/gcm or more. It is preferably 1.2×10 ⁴ to 1.0×10 ⁵ mL/gcm, even more preferably 1.3×10 ⁴ to 5.0×10 ⁴ mL/gcm. 0.5×10 ⁴ to 3.0×10 ⁴ mL/gcm is particularly preferred.

As the photopolymerization initiator a1, oxime compounds, aminoacetophenone compounds and acylphosphine compounds are preferred, oxime compounds and acylphosphine compounds are more preferred, and oxime compounds are even more preferred. In addition, the oxime compound has a high molar absorption coefficient and a high decomposition yield, has sufficient sensitivity, is moderately hydrophobic, and can improve the moisture resistance of the resulting film. and oxime compounds having a benzofuran skeleton are more preferred. When an oxime compound containing a fluorine atom is used as the photopolymerization initiator a1, it is particularly hydrophobic, and the moisture resistance of the resulting film can be further improved. Further, when an oxime compound having a benzofuran skeleton is used as the photopolymerization initiator a1, the effects of high decomposition yield and sufficient sensitivity can be obtained.

Specific examples of the photopolymerization initiator a1 include (C-13) and (C-15) shown in the above specific examples of the oxime compound. The photopolymerization initiator a1 may be used singly or in combination of two or more.

In the present invention, as photopolymerization initiators, the photopolymerization initiator a1 described above and the photopolymerization initiator a2 having an absorption coefficient of less than 8×10 ³ mL/gcm at a wavelength of 365 nm in methanol (hereinafter referred to as photoinitiator It is also preferable to use agent a2) in combination. By using the photopolymerization initiator a1 and the photopolymerization initiator a2 together, it is possible to form a pattern (pixels) with good adhesion to the support and a good shape. As the photopolymerization initiator a2, a compound having the absorption coefficient described above can be selected and used from the compounds described above.

The photopolymerization initiator a2 is preferably an oxime compound, a hydroxyacetophenone compound, a phenylglyoxylate compound, an aminoacetophenone compound, or an acylphosphine compound, more preferably an oxime compound, a hydroxyacetophenone compound, or a phenylglyoxylate compound, and an oxime compound. More preferred. Specific examples of the photopolymerization initiator a2 include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127, IRGACURE-907, IRGACURE-369, IRGACURE-379 , and IRGACURE-379EG (manufactured by BASF).

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass based on the total solid content of the colored photosensitive resin composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.

When the colored photosensitive resin composition of the present invention contains the photopolymerization initiator a2 described above, the content of the photopolymerization initiator a2 is 10 to 1000 parts by weight with respect to 100 parts by weight of the photopolymerization initiator a1. is preferred. The upper limit is preferably 500 parts by mass or less, more preferably 300 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more.

<<Solvent>>
The colored photosensitive resin composition of the present invention contains a solvent. An organic solvent is preferably used as the solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the colored photosensitive resin composition. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph number 0223 of International Publication WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (for example, 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a mass ppt (parts per trillion) level organic solvent may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The content of the solvent in the colored photosensitive resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 90% by mass.

<<Compound having an epoxy group>>
The colored photosensitive resin composition of the present invention can contain a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound preferably has 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably two or more. As the epoxy compound, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408. Compounds, compounds described in JP-A-2017-179172 can also be used. The contents of these are incorporated herein.

Epoxy compounds may be low molecular weight compounds (e.g. molecular weight less than 2000, further molecular weight less than 1000) or macromolecules (e.g. molecular weight 1000 or more, weight average molecular weight 1000 or more in the case of polymers). Either The weight average molecular weight of the epoxy compound is preferably 200-100,000, more preferably 500-50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

Examples of commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Corporation) and EPICLON N-695 (manufactured by DIC Corporation).

When the colored photosensitive resin composition of the present invention contains an epoxy compound, the content of the epoxy compound in the total solid content of the colored photosensitive resin composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, more preferably 10% by mass or less. One type of epoxy compound may be contained in the colored photosensitive resin composition, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Silane coupling agent>>
The colored photosensitive resin composition of the present invention can contain a silane coupling agent. According to this aspect, the adhesion of the obtained membrane to the support can be further improved. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred. Specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. the contents of which are incorporated herein.

The content of the silane coupling agent in the total solid content of the colored photosensitive resin composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The number of silane coupling agents may be one, or two or more. When two or more kinds are used, the total amount is preferably within the above range.

<<Curing accelerator>>
A curing accelerator may be added to the colored photosensitive resin composition of the present invention for the purpose of accelerating the reaction of the polymerizable monomer or lowering the curing temperature. Curing accelerators include methylol compounds (for example, compounds exemplified as crosslinking agents in paragraph number 0246 of JP-A-2015-34963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, JP-A Curing agent described in paragraph number 0186 of 2013-41165), a base generator (e.g., an ionic compound described in JP-A-2014-55114), a cyanate compound (e.g., JP-A-2012-150180 Compounds described in paragraph number 0071), alkoxysilane compounds (e.g., alkoxysilane compounds having an epoxy group described in JP-A-2011-253054), onium salt compounds (e.g., paragraph numbers of JP-A-2015-34963 0216 as examples of acid generators, compounds described in JP-A-2009-180949), and the like can also be used. When the colored photosensitive resin composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass in the total solid content of the colored photosensitive resin composition, 0 0.8 to 6.4% by mass is more preferred.

<<polymerization inhibitor>>
The colored photosensitive resin composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the colored photosensitive resin composition is preferably 0.0001 to 5% by mass.

<<Surfactant>>
The colored photosensitive resin composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicon surfactants can be used. For surfactants, reference can be made to paragraphs 0238 to 0245 of International Publication WO2015/166779, the contents of which are incorporated herein. In the present invention, the surfactant is preferably a fluorosurfactant. By incorporating a fluorine-based surfactant into the colored photosensitive resin composition, the liquid properties (especially fluidity) are further improved, and the liquid saving property can be further improved. In addition, it is possible to form a film with small thickness unevenness. The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in uniformity of the thickness of the coating film and liquid saving, and has good solubility in the colored photosensitive resin composition. .

As the fluorine-based surfactant, JP 2014-41318 Paragraph Nos. 0060-0064 (Corresponding International Publication No. 2014/17669 Paragraph Nos. 0060-0064) surfactants described in, JP 2011- 132503, paragraphs 0117-0132, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. .

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. For such fluorine-based surfactants, the description in JP-A-2016-216602 can be referred to, the content of which is incorporated herein.

上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 A block polymer can also be used as the fluorosurfactant. Examples thereof include compounds described in JP-A-2011-89090. The fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meta). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorosurfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol %.

A fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, such as Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorine-based surfactant.

The content of the surfactant in the total solid content of the colored photosensitive resin composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Ultraviolet absorber>>
The colored photosensitive resin composition of the present invention can contain an ultraviolet absorber. A conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used as the ultraviolet absorber. For details of these, paragraph numbers 0052 to 0072 of JP-A-2012-208374, paragraph numbers 0317-0334 of JP-A-2013-68814, paragraph numbers 0061-0080 of JP-A-2016-162946. The contents of which can be referred to are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). Further, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as the ultraviolet absorber. The content of the ultraviolet absorber in the total solid content of the colored photosensitive resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Antioxidant>>
The colored photosensitive resin composition of the present invention can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. The content of the antioxidant in the total solid content of the colored photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Other Ingredients>>
The colored photosensitive resin composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliary agents (e.g., conductive particles, fillers, erasers, etc.). foaming agents, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. Moreover, the colored photosensitive resin composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication WO2014/021023, International Publication WO2017/030005, and JP-A-2017-008219. Commercially available products include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.). Moreover, the colored photosensitive resin composition of the present invention may contain a light resistance improver.

The water content of the colored photosensitive resin composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably in the range of 0.1 to 1.0% by mass. preferable. The water content can be measured by the Karl Fischer method.

The colored photosensitive resin composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (such as flatness) and adjusting the film thickness. The viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa·s to 50 mPa·s, more preferably 0.5 mPa·s to 20 mPa·s at 25°C. As a method for measuring the viscosity, for example, a viscometer RE85L manufactured by Toki Sangyo Co., Ltd. (rotor: 1 ° 34' × R24, measurement range 0.6 to 1200 mPa s) is used, and the temperature is adjusted to 25 ° C. can be measured.

The colored photosensitive resin composition of the present invention can be preferably used as a colored photosensitive resin composition for forming colored pixels in a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. It can be more preferably used as a colored photosensitive resin composition for forming red pixels, green pixels or blue pixels, and further as a colored photosensitive resin composition for forming red pixels or a colored photosensitive resin composition for forming green pixels. It can be preferably used.

When the colored photosensitive resin composition of the present invention is used as a color filter for a liquid crystal display device, the voltage holding ratio of the liquid crystal display device provided with the color filter is preferably 70% or more, and preferably 90% or more. is more preferred. Known means for obtaining a high voltage holding ratio can be appropriately incorporated, and typical means are the use of highly pure materials (e.g., reduction of ionic impurities) and the control of the amount of acidic functional groups in the composition. is mentioned. The voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of JP-A-2011-008004 and paragraphs 0123 to 0129 of JP-A-2012-224847.

The container for the colored photosensitive resin composition of the present invention is not particularly limited, and known containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.

<Method for preparing colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention can be prepared by mixing the aforementioned components. In preparing the colored photosensitive resin composition, all the components may be simultaneously dissolved and/or dispersed in an organic solvent to prepare the colored photosensitive resin composition, or if necessary, each component may be appropriately mixed in two. The above solutions or dispersions may be mixed at the time of use (at the time of coating) to prepare a colored photosensitive resin composition.

Moreover, it is preferable that a process of dispersing a pigment is included in the preparation of the colored photosensitive resin composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing pigments are described in ``Dispersion Technology Encyclopedia, Information Organization Co., Ltd., July 15, 2005'' and ``Dispersion Technology Centered on Suspension (Solid/Liquid Dispersion System) and Industrial Applications'' The process and disperser described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the pigment, the particles may be made finer in the salt milling step. Materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.

In preparation of the colored photosensitive resin composition, it is preferable to filter the colored photosensitive resin composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyethylene, polyolefin resins such as polypropylene (PP) (high density, ultra high molecular weight including polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like can be used as filters.

It is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.

<Membrane>
The film of the present invention is a film obtained from the colored photosensitive resin composition of the present invention described above. The film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Red pixels, green pixels, and blue pixels are preferred, and green pixels and red pixels are more preferred. Green pixels are more preferred. The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

<Color filter>
Next, the color filter of the present invention will be explained. The color filter of the invention has the film of the invention described above. More preferably, it has the film of the present invention as a pixel of a color filter. The color filter of the present invention can be used for solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), image display devices, and the like.

In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

The color filter of the present invention preferably has a pixel width of 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, more preferably 10.0 μm or less. Also, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco. Also, the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.). Moreover, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω·cm or more, more preferably 10 ¹¹ Ω·cm or more. Although the upper limit is not specified, it is preferably 10 ¹⁴ Ω·cm or less, for example. The volume resistance value of the pixel can be measured using, for example, a super-high resistance meter 5410 (manufactured by Advantest).

Also, in the color filter of the present invention, a protective layer may be provided on the surface of the film of the present invention. By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01-10 μm, more preferably 0.1-5 μm. Examples of the method of forming the protective layer include a method of applying a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides. Resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ and the like, and two or more of these components may be contained. For example, in the case of a protective layer intended to block oxygen, the protective layer preferably contains a _polyol resin, _SiO2 , _Si2N4 . In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin or a fluororesin.

When a resin composition is applied to form a protective layer, known methods such as spin coating, casting, screen printing, and ink-jetting can be used as methods for applying the resin composition. Known organic solvents (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When the protective layer is formed by a chemical vapor deposition method, the chemical vapor deposition method includes known chemical vapor deposition methods (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method). can be used.

If necessary, the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain. Examples of organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. A known absorber can be used as the absorber for light of a specific wavelength. Examples of the ultraviolet absorbent and the near-infrared absorbent include the materials described above. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total weight of the protective layer.

As the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each color pixel. Moreover, the partition wall may be formed with the configuration described in US2018/0040656.

<Manufacturing method of color filter>
Next, a method for manufacturing the color filter of the present invention will be described. The color filter of the present invention comprises the steps of forming a colored photosensitive resin composition layer on a support using the above-described colored photosensitive resin composition of the present invention, and forming a colored photosensitive resin composition layer on the colored photosensitive resin composition layer by a photolithography method. and a step of forming a pattern on the substrate.

Pattern formation by photolithography includes a step of forming a colored photosensitive resin composition layer on a support using the colored photosensitive resin composition of the present invention, and patternwise exposing the colored photosensitive resin composition layer. and a step of developing and removing unexposed portions of the colored photosensitive resin composition layer to form a pattern (pixels). If necessary, a step of baking the colored photosensitive resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

In the step of forming a colored photosensitive resin composition layer, the colored photosensitive resin composition of the present invention is used to form a colored photosensitive resin composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. In some cases, the silicon substrate is formed with a black matrix that isolates each pixel. In addition, the silicon substrate may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the substrate surface.

A known method can be used as a method for applying the colored photosensitive resin composition. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the method of applying the colored photosensitive resin composition, the descriptions in International Publication WO2017/030174 and International Publication WO2017/018419 can be referred to, and the contents thereof are incorporated herein.

The colored photosensitive resin composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process. When pre-baking is performed, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher. The pre-bake time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, even more preferably 80 to 2200 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

Next, the colored photosensitive resin composition layer is patternwise exposed (exposure step). For example, the colored photosensitive resin composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable. A long-wave light source of 300 nm or more can also be used.

The dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be selected as appropriate, and in addition to exposure in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free) or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m ² to 100000 W/m ² (eg, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). can be done. The oxygen concentration and exposure illuminance may be appropriately combined. For example, the illuminance may be 10000 W/m ² at an oxygen concentration of 10% by volume and 20000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed portion of the colored photosensitive resin composition layer is removed by development to form a pattern (pixels). The development and removal of the unexposed portion of the colored photosensitive resin composition layer can be performed using a developer. As a result, the unexposed portion of the colored photosensitive resin composition layer in the exposure step is eluted into the developer, leaving only the photocured portion. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

Examples of the developer include organic solvents and alkaline developers. The alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene. Alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. Examples of surfactants include the surfactants described above, and nonionic surfactants are preferred. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the colored photosensitive resin composition layer after development while rotating the support on which the colored photosensitive resin composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.

After development, it is preferable to carry out additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Further, the additional exposure processing may be performed by the method described in KR1020170122130A.

<Structure>
Next, the structure of the present invention will be described with reference to the drawings. FIG. 1 is a side cross-sectional view showing one embodiment of the structure of the present invention, and FIG. 2 is a plan view of the support member in the same structure viewed from directly above.
As shown in FIGS. 1 and 2, the structure 100 of the present invention includes a support 1, partition walls 2 provided on the support 1, and regions on the support 1 partitioned by the partition walls 2. and a colored layer 4 provided. At least one type (one color) of the colored layer 4 is obtained using the above-described colored photosensitive resin composition of the present invention.

In the structure of the present invention, the type of support 1 is not particularly limited. Substrates (silicon wafers, silicon carbide wafers, silicon nitride wafers, sapphire wafers, glass wafers, etc.) used in various electronic devices such as solid-state imaging devices can be used. Further, a substrate for a solid-state imaging device on which a photodiode is formed, or the like can also be used. Further, if necessary, an undercoat layer may be provided on these substrates for improving the adhesion to the upper layer, preventing the diffusion of substances, or flattening the surface.

As shown in FIG. 1, partition walls 2 are formed on the support 110 . In this embodiment, as shown in FIG. 2, the partition walls 2 are formed in a grid pattern in a plan view seen from directly above the support 1 . In this embodiment, the shape of the region partitioned by the partition walls 2 on the support 110 (hereinafter also referred to as the shape of the partition opening) is a square. It is not particularly limited, and may be, for example, rectangular, circular, elliptical, or polygonal.

Although the material of the partition wall 2 is not particularly limited, it is preferably formed of a material having a lower refractive index than that of the colored layer 4 . According to this aspect, a structure in which the colored layer 4 with a high refractive index is surrounded by the partition walls 2 with a low refractive index can be obtained. By doing so, the light that is about to leak from the colored layer 4 having a large refractive index is reflected by the partition wall 2 and is easily returned to the colored layer 4, thereby preventing the light from leaking to the adjacent colored layer 4. can be suppressed. As specific examples of the material of the partition wall 2, various inorganic materials and organic materials can be used. Examples of organic materials include acrylic resins, polystyrene resins, polyimide resins, and organic SOG (Spin On Glass) resins. Examples of inorganic materials include porous silica, polycrystalline silicon, silicon oxide, silicon nitride, and metallic materials such as tungsten and aluminum.

The width W1 of the partition wall 2 is preferably 20 to 500 nm. The lower limit is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.
Moreover, the height H1 of the partition wall 2 is preferably 200 nm or more, more preferably 300 nm or more, and even more preferably 400 nm or more. The upper limit is preferably the thickness of the colored layer 4 x 200% or less, more preferably the thickness of the colored layer 4 x 150% or less, and is substantially the same as the thickness of the colored layer 4. More preferred.
The ratio of height to width (height/width) of the partition walls 2 is preferably 1-100, more preferably 5-50, and even more preferably 5-30.

A colored layer 4 is formed on the support 1 in a region defined by the partition wall 2 (opening of the partition wall). The type of the colored layer 4 is not particularly limited. Colored layers such as red, blue, green, magenta, and cyan are included. The color and arrangement of the colored layers can be arbitrarily selected. Pixels other than the colored layer may be further formed in the regions partitioned by the partition walls 2 . Pixels other than the colored layer include transparent pixels and pixels of an infrared transmission filter.

The width L1 of the colored layer 4 can be appropriately selected depending on the application. For example, for high-pixel solid-state imaging devices, the thickness is preferably 500 to 2000 nm, more preferably 500 to 1500 nm, even more preferably 500 to 1000 nm.
The height (thickness) H2 of the colored layer 4 can be appropriately selected depending on the application. For example, for high-pixel solid-state imaging devices, it is preferably 300 to 1000 nm, more preferably 300 to 800 nm, even more preferably 300 to 600 nm. The height H2 of the colored layer 4 is preferably 50 to 150%, more preferably 70 to 130%, and even more preferably 90 to 110% of the height H1 of the partition wall 2.

In the structure of the present invention, it is also preferable that a protective layer is provided on the surfaces of the partition walls. By providing the protective layer on the surface of the partition wall 2, the adhesion between the partition wall 2 and the colored layer 4 can be improved. Various inorganic materials and organic materials can be used as the material of the protective layer. Examples of organic materials include acrylic resins, polystyrene resins, polyimide resins, and organic SOG (Spin On Glass) resins. It can also be formed using a composition containing a compound having an ethylenically unsaturated group.

The structure of the present invention can be preferably used for color filters, solid-state imaging devices, image display devices, and the like.

<Solid-state image sensor>
The solid-state imaging device of the present invention has the film 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 the film of the present invention and functions as a solid-state imaging device.

A plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication WO2018/043654. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.

<Image display device>
The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. For a definition of an image display device and details of each image display device, see, for example, "Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to liquid crystal display devices of various systems described in the above-mentioned "next generation liquid crystal display technology".

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) according to the following conditions.
Column type: Column connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 Developing solvent: Tetrahydrofuran Column temperature: 40°C
Flow rate (sample injection volume): 1.0 μL (sample concentration 0.1% by mass)
Apparatus name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve Base resin: polystyrene resin

<Method for measuring acid value>
The acid value of a resin represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. The acid value of the resin was measured as follows. That is, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and the resulting solution was measured using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) at 25 °C. was neutralized and titrated with a 0.1 mol/L sodium hydroxide aqueous solution. Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated by the following formula.
A = 56.11 x Vs x 0.5 x f/w
A: Acid value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L aqueous sodium hydroxide solution required for titration
f: titer of 0.1 mol / L sodium hydroxide aqueous solution w: mass of measurement sample (g) (converted to solid content)

<Synthesis of Resin>
(Synthesis of Resin B-1) (Resin Having Aromatic Carboxyl Group)
50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into a reaction vessel, and the atmospheric gas was replaced with nitrogen gas. Heat the inside of the reaction vessel to 70 ° C., add 6 parts by mass of 3-mercapto-1,2-propanediol, further add 0.12 parts by mass of AIBN (azobisisobutyronitrile), reacted over time. Solid content measurement confirmed that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.8 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst. 20 parts by mass was added and reacted at 120° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMEA was added to adjust the non-volatile content (solid content concentration) to 20% by mass to obtain a resin solution of resin B-1 having an acid value of 43 mgKOH/g and a weight average molecular weight (Mw) of 9000.

(Synthesis of Resin B-2) (Resin Having Aromatic Carboxyl Group)
50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate, and 45.4 parts by mass of PGMEA were charged into a reaction vessel, and the atmospheric gas was replaced with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts by mass of 3-mercapto-1,2-propanediol was added, and 0.12 parts by mass of AIBN was further added and reacted for 12 hours. Solid content measurement confirmed that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU as a catalyst were added and reacted at 120° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMEA was added to adjust the nonvolatile content (solid content concentration) to 20% by mass to obtain a resin solution of resin B-2 having an acid value of 43 mgKOH/g and a weight average molecular weight (Mw) of 9000.

(Synthesis of Resin B-3) (Resin Having Aromatic Carboxyl Group)
In the synthesis of resin B-2, in the same manner, except that 20 parts by mass of t-butyl methacrylate was changed to 20 parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, acid value 43 mgKOH / g, weight A resin solution of resin B-3 having an average molecular weight (Mw) of 9000 (solid content concentration of 20% by mass) was obtained.

(Synthesis of Resin B-4) (Resin Having Aromatic Carboxyl Group)
In the synthesis of resin B-2, 20 parts by mass of t-butyl methacrylate was added to 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenzu MOI-BM, manufactured by Showa Denko K.K. , a blocked isocyanate monomer) was changed to 20 parts by mass in the same manner as above, and a resin solution (solid content concentration 20% by mass) of resin B-4 having an acid value of 43 mgKOH/g and a weight average molecular weight (Mw) of 9000 was obtained. .

(Synthesis of Resin B-5) (Resin Having Aromatic Carboxyl Group)
A reaction vessel was charged with 6.0 parts by mass of 3-mercapto-1,2-propanediol, 9.5 parts by mass of pyromellitic anhydride, 62 parts by mass of PGMEA, and 0.2 parts by mass of DBU. , the atmospheric gas was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the temperature in the system is cooled to 70 ° C., 65 parts by mass of methyl methacrylate and 5.0 parts by mass of ethyl acrylate. part, 15 parts by mass of t-butyl acrylate, 5.0 parts by mass of methacrylic acid, 10 parts by mass of hydroxyethyl methacrylate, and 53.5 parts by mass of a PGMEA solution in which 0.1 parts by mass of AIBN are dissolved was added and reacted for 10 hours. After confirming that the polymerization had progressed by 95% by measuring the solid content, the reaction was terminated. PGMEA was added to adjust the nonvolatile content (solid content concentration) to 20% by mass to obtain a resin solution of resin B-5 having an acid value of 70.5 mgKOH/g and a weight average molecular weight (Mw) of 10,000.

(Synthesis of Resin B-6) (Resin Having Aromatic Carboxyl Group)
108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, 650 parts by mass of methoxypropyl acetate, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged into a reaction vessel, and the atmospheric gas was introduced. After purging with nitrogen gas, reaction was carried out at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts by mass of the compound obtained in the first step in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, 200 parts by mass of 2-methoxyethyl acrylate, 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA were charged into a reaction vessel, and the inside of the reaction vessel was heated to 80 ° C. ,2′-azobis(2,4-dimethylvaleronitrile) was added and reacted for 12 hours (second step). Solid content measurement confirmed that 95% had reacted. Finally, 500 parts by mass of a 50% by mass PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate, and 0.1 part by mass of hydroquinone were charged into a reaction vessel, isocyanate The reaction was carried out until the disappearance of the 2270 cm ^-1 peak based on the group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled, PGMEA was added to adjust the nonvolatile content (solid content concentration) to 20% by mass, the acid value was 68 mgKOH / g, the unsaturated double bond value was 0.62 mmol / g, A resin solution of resin B-6 having a weight average molecular weight (Mw) of 13,000 was obtained.

(Synthesis of Resin C-1) (Resin Containing Repeating Units Derived from Compound Represented by Formula (I) and Repeating Units Derived from Alkyl (Meth)acrylate)
Put 370 parts by mass of cyclohexanone in a reaction vessel, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 38 parts by mass of methacrylic acid, 6 parts by mass of 2-hydroxyethyl methacrylate, and benzyl methacrylate. 21 parts by mass, 16 parts by mass of n-butyl methacrylate, 21 parts by mass of paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd., Aronix M110), and 0.4 parts by mass of AIBN. The polymerization reaction was carried out by adding dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further carried out at 80° C. for 3 hours, then 0.2 parts by mass of AIBN dissolved in 10 parts by mass of cyclohexanone was added, and the reaction was further continued at 80° C. for 1 hour to obtain a resin solution. Obtained. After cooling this resin solution to room temperature, about 2 g was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. A solution of resin C-1 having an acid value of 230 mgKOH/g was prepared by adding cyclohexanone so that

(Synthesis of Resin C-2) (Resin Containing Repeating Units Derived from Compound Represented by Formula (I) and Repeating Units Derived from Alkyl (Meth)acrylate)
28 parts by mass of methacrylic acid, 8.5 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of benzyl methacrylate, 18 parts by mass of n-butyl methacrylate, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd., Aronix M110) was changed to 23 parts by mass, and the synthesis and non-volatile content (solid content concentration) were adjusted in the same manner as for Resin C-1 to prepare a solution of Resin C-2 having an acid value of 160 mgKOH/g.

(Synthesis of Resin C-3) (Resin Containing Repeating Units Derived from Compound Represented by Formula (I) and Repeating Units Derived from Alkyl (Meth)acrylate)
70.0 parts by mass of PGMEA was charged in a reaction vessel, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen, then 13.3 parts by mass of n-butyl methacrylate and 4.6 parts by mass of 2-hydroxyethyl methacrylate. and 4.3 parts by mass of methacrylic acid, 7.4 parts by mass of paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd., Aronix M110), and 0.4 parts by mass of AIBN. It dripped over time. After completion of dropping, the reaction was continued for 3 hours to obtain a resin solution. After cooling this resin solution to room temperature, about 2 g was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. A solution of resin C-3 having a weight average molecular weight (Mw) of 26,000 was prepared by adding PGMEA so that

<Preparation of pigment dispersion>
After mixing the raw materials shown in the table below, 230 parts by mass of zirconia beads with a diameter of 0.3 mm are added, and dispersion treatment is performed using a paint shaker for 5 hours, and the beads are separated by filtration to produce a pigment dispersion. bottom. Numerical values indicating compounding amounts in the following table are parts by mass. The value of the compounding amount of the resin (dispersant) is the value of the compounding amount in a resin solution having a solid content of 20% by mass.

The abbreviations in the above table are as follows.
(pigment)
PR254: C.I. I. Pigment Red 254
PR264: C.I. I. Pigment Red 264
PR272: C.I. I. Pigment Red 272
PR122: C.I. I. Pigment Red 122
PO71: C.I. I. Pigment Orange 71
PG58: C.I. I. Pigment Green 58
PG36: C.I. I. Pigment Green 36
PG7: C.I. I. Pigment Green 7
PG59: C.I. I. Pigment Green 59
PG62: C.I. I. Pigment Green 62
PG63: C.I. I. Pigment Green 63
PY139: C.I. I. Pigment Yellow 139
PY150: C.I. I. Pigment Yellow 150
PY185: C.I. I. Pigment Yellow 185
PG15:6: C.I. I. Pigment Blue 15:6
PV23: C.I. I. Pigment Violet 23

(pigment derivative)
Derivatives 1 to 5: compounds having the following structures

(Resin (dispersant))
B-1 to B-6: Resin solutions of the resins B-1 to B-6 described above

<Preparation of colored photosensitive resin composition>
A colored photosensitive resin composition was prepared by mixing the raw materials shown in the table below. The value of the colorant concentration in the table below is the content of the colorant (the total content of the pigment and the pigment derivative) in the total solid content of the colored photosensitive resin composition. Further, the values of the compounding amounts of the resins C-1 to C-5 are the values of the compounding amounts in resin solutions having a solid content of 20% by mass.

The abbreviations in the above table are as follows.
(Pigment dispersion)
Dispersions R1 to R11: Dispersions R1 to R11 described above
Dispersions G1 to G15: Dispersions G1 to G15 as described above
Dispersions B1 to B3: Dispersions B1 to B3 described above
(resin)
C-1: Resin solution of resin C-1 described above (solid content concentration 20% by mass)
C-2: Resin solution of resin C-2 described above (solid content concentration 20% by mass)
C-3: Resin solution of resin C-3 described above (solid content concentration 20% by mass)
C-4: 20% by mass PGMEA solution of a resin having the following structure (numerical values attached to the main chain are molar ratios, Mw = 38000)
C-5: 20% by mass PGMEA solution of a resin having the following structure (the numerical value attached to the main chain is the molar ratio, Mw = 30000)

(Polymerizable monomer)
E-1: Aronix M402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
E-2: Aronix M520 (manufactured by Toagosei Co., Ltd., an acrylate compound having an acid group)
E-3: NK ester A-TMMT (Shin-Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)
E-4: Aronix TO-2349 (manufactured by Toagosei Co., Ltd.)

(Photoinitiator)
G-1: compound with the following structure (absorbance coefficient at wavelength 365 nm in methanol = 18900 mL/gcm)
G-2: compound with the following structure (absorbance coefficient at wavelength 365 nm in methanol = 11000 mL/gcm)
G-3: compound with the following structure (absorbance coefficient at wavelength 365 nm in methanol = 7749 mL/gcm)
G-4: compound with the following structure (absorbance coefficient at wavelength 365 nm in methanol = 810 mL/gcm)

（重合禁止剤）
Ｊ―１：ｐ－メトキシフェノール
（溶剤）
Ｋ－１：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）
Ｋ－２：酢酸ブチル (Surfactant)
I-1: 1 wt% PGMEA solution of the following mixture (Mw = 14000). In the following formula, % indicating the ratio of repeating units is % by mass.

(polymerization inhibitor)
J-1: p-methoxyphenol (solvent)
K-1: PGMEA (propylene glycol monomethyl ether acetate)
K-2: butyl acetate

<Performance evaluation>
(Evaluation of moisture resistance)
On a silicon wafer, the colored photosensitive resin composition is applied using a spin coater so that the film thickness after prebaking becomes the film thickness shown in the table below, and heat-treated for 120 seconds using a hot plate at 100 ° C. ( pre-baking) was performed. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm is exposed at an exposure amount of 500 mJ/cm ² , and then heated using a hot plate at 220° C. for 300 seconds. Processing (post-baking) was performed. The resulting film was placed in a thermo-hygrostat at 130° C. and humidity of 85%, taken out after 96 hours, placed in an environment of 23° C. and humidity of 60% for 2 hours, and then the film thickness was measured. Moisture resistance was evaluated according to the following criteria.
[Film thickness after being put into the constant temperature and humidity chamber]/[Film thickness before being put into the constant temperature and humidity chamber]=X, moisture resistance was evaluated according to the following criteria.
A: X≧0.9
B: 0.8≤X<0.9
C: 0.7≤X<0.8
D: X<0.7

(Evaluation of retention property)
A CT-4000L solution (manufactured by Fuji Film Electronic Materials Co., Ltd.; transparent base material) is applied on a silicon wafer so that the dry film thickness is 0.1 μm, and dried to form a transparent film. A heat treatment was performed at 220° C. for 5 minutes.
The colored photosensitive resin composition was applied using a spin coater so that the film thickness after prebaking was as shown in the table below, and heat treatment (prebaking) was performed using a hot plate at 100 ° C. for 120 seconds. . Next, an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used to 365 nm through a mask pattern in which square pixels each having a side of 1.1 μm were arranged in an area of 4 mm×3 mm on a silicon wafer. was exposed to light with a wavelength of 500 mJ/cm ² .
In order to evaluate the retention property after the exposure, the above silicon wafers were stored for 7 days in a light-shielded state (retention processing) and those not stored were prepared.
A silicon wafer having an exposed composition layer (silicon wafer after the holding treatment for those subjected to the holding treatment, silicon wafer after the exposure for those not carrying out the holding treatment) is subjected to a spin shower developing machine (DW- 30 type, manufactured by Chemitronics Co., Ltd.), paddle-developed using CD-2000 (manufactured by Fuji Film Electronic Materials Co., Ltd.) at 23° C. for 60 seconds, and rotated by a rotating device. While rotating the silicon wafer at a rotation speed of 50 rpm, pure water is supplied from above the center of rotation in a shower from a jetting nozzle to perform a rinse treatment, and then a heat treatment is performed using a hot plate at 220° C. for 300 seconds (post-baking). ) was performed.
The number of defects in the obtained colored pattern film was inspected using a wafer defect evaluation apparatus ComPLUS3 manufactured by AMAT. Evaluation was performed according to the following criteria.
When [the number of defects in the film with the retention treatment]−[the number of defects in the film without the retention treatment]=Y, the retention property was evaluated according to the following criteria.
A: Y≤10
B: 10<Y≤50
C: 50<Y≦200
D:Y>200

As shown in the table above, the examples were evaluated favorably in terms of moisture resistance and storage properties.
In each example, the same effect can be obtained even if the polymerization inhibitor and surfactant are replaced with the compounds described in the specification.

(Example 100)
A green composition was applied onto a silicon wafer by a spin coating method so that the film thickness after forming the film would be 1.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at an exposure amount of 1,000 mJ/cm ² through a 2 μm square dot pattern mask. Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, the green composition was patterned by heating at 200° C. for 5 minutes using a hot plate. Similarly, the Red composition and the Blue composition were sequentially patterned to form green, red and blue colored patterns (Bayer patterns).
As the green composition, the colored photosensitive resin composition of Example 24 was used.
The Red composition and the Blue composition will be described later.
Note that the Bayer pattern is one red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. ) elements.
The obtained color filter was incorporated into a solid-state imaging device according to a known method. This solid-state imaging device had a favorable image recognition ability.

- Red composition -
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a red composition.
Red pigment dispersion: 51.7 parts by mass Resin 101: 0.6 parts by mass Polymerizable compound 102: 0.6 parts by mass Photopolymerization initiator 101: 0.3 parts by mass Surfactant 101: 4.2 parts by mass PGMEA : 42.6 parts by mass

-Blue composition-
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.
Blue pigment dispersion: 44.9 parts by mass Resin 101: 2.1 parts by mass Polymerizable compound 101: 1.5 parts by mass Polymerizable compound 102: 0.7 parts by mass Photoinitiator 101: 0.8 parts by mass Interface Active agent 101: 4.2 parts by mass PGMEA: 45.8 parts by mass

Raw materials used for the Red composition and the Blue composition are as follows.

Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. A mixture of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was passed through a bead mill (zirconia beads with a diameter of 0.3 mm). ) for 3 hours. Thereafter, dispersion treatment was further performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under a pressure of 2,000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

Blue pigment dispersion C.I. I. Pigment Blue 15:6, 9.7 parts by mass, C.I. I. A mixture of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was prepared in a bead mill (zirconia beads with a diameter of 0.3 mm). was mixed and dispersed for 3 hours. Thereafter, dispersion treatment was further performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under a pressure of 2,000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion.

重合性化合物１０１：ＫＡＹＡＲＡＤ ＤＰＨＡ（日本化薬（株）製）
重合性化合物１０２：下記構造の化合物

光重合開始剤１０１：ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ製）
界面活性剤１０１：下記混合物（Ｍｗ＝１４０００）の１質量％ＰＧＭＥＡ溶液。下記の式中、繰り返し単位の割合を示す％はモル％である。

Resin 101: A 40% by mass PGMEA solution of a resin having the following structure (numerical values attached to the main chain are molar ratios, Mw = 14000)

Polymerizable compound 101: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound 102: compound having the following structure

Photoinitiator 101: IRGACURE-OXE02 (manufactured by BASF)
Surfactant 101: 1 wt% PGMEA solution of the following mixture (Mw = 14000). In the following formulas, % indicating the ratio of repeating units is mol %.

110: Support, 2: Partition, 4: Colored layer, 100: Structure

Claims (17)

A colored photosensitive resin composition containing a coloring material, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent,
The photopolymerization initiator contains a photopolymerization initiator a1 having an absorption coefficient of 8×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol,
The photopolymerization initiator a1 is an oxime compound containing a fluorine atom,
The resin includes a resin b1 containing a repeating unit b1-1 derived from a compound represented by the following formula (III) and a repeating unit b1-2 derived from an alkyl (meth)acrylate;
containing a resin b2 having an aromatic carboxyl group,
colored photosensitive resin composition;

In formula (III), R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0-15. A colored photosensitive resin composition containing a coloring material, a resin, a polymerizable monomer, a photopolymerization initiator and a solvent,
The coloring material is C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I. I. Pigment Red 272, C.I. I. Pigment Red 122, C.I. I. Pigment Orange 71, C.I. I. Pigment Green 36, C.I. I. Pigment Green 7, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, C.I. I. Pigment Blue 15:6 and C.I. I. at least one selected from Pigment Violet 23,
The photopolymerization initiator contains a photopolymerization initiator a1 having an absorption coefficient of 8×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol,
The photopolymerization initiator a1 is an oxime compound containing a fluorine atom,
The resin contains a resin b1 containing a repeating unit b1-1 derived from a compound represented by the following formula (III) and a repeating unit b1-2 derived from an alkyl (meth)acrylate,
The content of the polymerizable monomer is 2 to 20% by mass in the total solid content of the colored photosensitive resin composition,
colored photosensitive resin composition;

In formula (III), R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0-15. 3. The colored photosensitive resin according to claim 1, wherein the resin b1 contains 1 to 70 mol % of the repeating unit b1-1 and 1 to 70 mol % of the repeating unit b1-2 in all repeating units. Composition. 3. The colored photosensitive resin composition according to claim 2, wherein the resin further contains a resin b2 having an aromatic carboxyl group. The colored photosensitive resin composition according to claim 1 or 4, wherein the resin b2 is a resin containing a repeating unit represented by the following formula (b2-1);

In the formula, Ar ¹ represents a group containing an aromatic carboxyl group, L ¹ represents --COO-- or --CONH--, and L ² represents a divalent linking group. 2. The colored photosensitive resin composition according to claim 1, wherein said colorant contains a pigment. 7. The colored photosensitive resin composition according to claim 6, wherein said pigment contains at least one selected from diketopyrrolopyrrole compounds and phthalocyanine compounds. 3. The colored photosensitive resin composition according to claim 1, wherein the polymerizable monomer contains a polymerizable monomer having an acid group. The colored photosensitive resin composition according to any one of claims 1 to 8, which is used for color filters. The colored photosensitive resin composition according to any one of claims 1 to 9, which is used for solid-state imaging devices. The colored photosensitive resin composition according to any one of claims 1 to 10, which is used to form a colored layer in regions partitioned by partition walls. A film obtained from the colored photosensitive resin composition according to any one of claims 1 to 11. A color filter comprising the film according to claim 12 . A step of forming a colored photosensitive resin composition layer on a support using the colored photosensitive resin composition according to any one of claims 1 to 11, and a colored photosensitive resin composition layer by a photolithographic method. and forming a pattern on the color filter. a support;
a partition provided on the support;
A structure having a colored layer obtained from the colored photosensitive resin composition according to any one of claims 1 to 11 provided on a support in a region partitioned by partition walls. A solid-state imaging device comprising the film according to claim 12 . An image display device comprising the film according to claim 12 .

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