JP2018205605A - Coloring photosensitive resin composition, cured product, organic electroluminescent element, image display device and illumination - Google Patents

Abstract

To provide a coloring photosensitive resin composition for forming a partition wall of an organic electroluminescent element, where the coloring photosensitive resin composition can prevent the occurrence of a non-light emission region in the vicinity of the partition wall of a light emitter.SOLUTION: A coloring photosensitive resin composition for forming a partition wall of an organic electroluminescent element contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound, (e) a solvent, and (f) a dispersant. The (f) dispersant contains an acidic group and a basic group.SELECTED DRAWING: None

Description

  The present invention relates to a colored photosensitive composition and the like. More specifically, for example, a colored photosensitive resin composition preferably used for forming partition walls in an organic electroluminescent device, a cured product composed of the colored photosensitive resin composition, an organic electroluminescent device comprising the cured product, The present invention relates to an image display device and illumination.

  An organic electroluminescence (organic EL (Electro-Luminescence)) element is self-luminous, unlike a liquid crystal display device, and is therefore excellent in black expression and greatly improved in contrast. At present, transparent materials are used for the partition walls that partition the pixels, so that there is a problem of deterioration of contrast due to reflection of external light or stray light between pixels. In view of this, the use of colored barrier ribs in which the barrier rib material has a light-shielding property has been studied.

  For example, Patent Document 1 discloses that a fine line pattern and a fine contact hole are obtained by using a negative photosensitive resin composition having a specific content of solid acid value using a specific alkali-soluble resin and a black organic pigment. It is described that a partition wall having both can be formed.

International Publication No. 2013/069789 Pamphlet

  The organic electroluminescence device emits light by passing a current through a light emitting portion stacked in an opening between partition walls. At this time, the light emitting portion needs to emit light uniformly, and the luminance decreases when a non-light emitting region is generated in the vicinity of the partition wall. Therefore, the partition of the organic electroluminescent element is required not to inhibit the light emission of the light emitting part.

  When the present inventors examined the colored photosensitive resin composition described in Patent Document 1, depending on the type of the dispersant, when the organic electroluminescence device was produced, a non-light emitting region was formed in the vicinity of the partition wall of the light emitting portion. It was found to occur.

  Accordingly, the present invention provides a colored photosensitive resin composition for forming a partition wall of an organic electroluminescence device, and capable of suppressing the generation of a non-light emitting region in the vicinity of the partition wall of a light emitting part. For the purpose.

  As a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be solved by using a specific dispersant, and the present invention has been completed. That is, the gist of the present invention is as follows.

[1] An organic electroluminescent device comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound, (e) a solvent, and (f) a dispersant. A colored photosensitive resin composition for forming a partition wall of
The colored photosensitive resin composition, wherein the dispersant (f) contains an acidic group and a basic group.

[2] The colored photosensitive resin composition according to [1], wherein the (a) colorant contains an organic black pigment.
[3] The organic black pigment contains a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound. The colored photosensitive resin composition as described.

(In formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N = CH ₂ , N = CHR ¹¹ , N = CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
And at least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number. 2 to 12 alkynyl groups. )

[4] The colored photosensitive composition according to any one of [1] to [3], wherein (a) the colorant contains at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment, and a purple pigment. Resin composition.
[5] In the above [4], (a) the colorant contains at least one selected from the group consisting of a red pigment and an orange pigment and at least one selected from the group consisting of a blue pigment and a purple pigment. The colored photosensitive resin composition as described.

[6] The colored photosensitive resin composition according to any one of [1] to [5], wherein the basic group contained in the dispersant (f) is a tertiary amino group or a quaternary ammonium base.
[7] The colored photosensitive resin composition according to any one of [1] to [6], wherein the acidic group contained in the dispersant (f) is a phosphoric acid group.

[8] The colored photosensitive resin composition according to any one of [1] to [7], wherein an optical density per 1 μm film thickness of the cured coating film is 1.0 or more.
[9] A cured product composed of the colored photosensitive resin composition according to any one of [1] to [8].

[10] An organic electroluminescence device comprising the cured product according to [9].
[11] An image display device comprising the organic electroluminescent element according to [10].
[12] An illumination including the organic electroluminescent element according to [10].

[13] A pigment dispersion for producing a colored photosensitive resin composition for forming a partition wall of an organic electroluminescence device containing (a) a colorant, (e) a solvent, and (f) a dispersant,
The pigment dispersion liquid, wherein the dispersant (f) contains an acidic group and a basic group.

  According to the present invention, there is provided a colored photosensitive resin composition for forming a partition wall of an organic electroluminescent device, which can suppress generation of a non-light emitting region in the vicinity of the partition wall of a light emitting part. Can do.

FIG. 1 is an optical microscope observation result of the organic electroluminescent element of Comparative Example 1. FIG. 2 is an optical microscope observation result of the organic electroluminescent element of Example 1. FIG. 3 is an optical microscope observation result of the organic electroluminescent element of Example 2.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.

  The term “(co) polymer” means to include both a single polymer (homopolymer) and a copolymer (copolymer). “Acid (anhydride)”, “(anhydrous) ... acid” , Is meant to include both acids and anhydrides. In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.

In the present invention, the term “monomer” is a term corresponding to a so-called high molecular substance (polymer), and includes a dimer, a trimer, an oligomer, etc. in addition to a narrowly defined monomer (monomer). It is.
In the present invention, the “total solid content” means all components other than the solvent contained in the colored photosensitive resin composition or in the ink described later.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.
On the other hand, unless otherwise specified, the “acid value” represents an acid value in terms of effective solid content, and is represented by the mass of an acid group and an equivalent amount of KOH per 1 g of the solid content of the dispersant or alkali-soluble resin. It is a value and is calculated by neutralization titration according to the description of JIS K 0070-1992.

  In the present specification, the percentage and part expressed by “mass” are synonymous with the percentage and part expressed by “weight”.

[Colored photosensitive resin composition]
The colored photosensitive resin composition of the present invention is for forming partition walls of an organic electroluminescent device, and comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d ) Photopolymerizable compound, (e) Solvent and (f) Dispersant as essential components, and if necessary, adhesion improver such as silane coupling agent, applicability improver, development improver, UV absorption Including other compounding components such as an agent, an antioxidant, a surfactant, and a pigment derivative, each compounding component is usually used in a state dissolved or dispersed in a solvent.

<(A) Colorant>
The colored photosensitive resin composition of the present invention contains (a) a colorant. (A) By containing a colorant, it is possible to obtain an appropriate light-absorbing property, particularly when used for an application for forming a light-shielding member such as a colored partition.
(A) As the colorant, a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.
(A) The pigment contained in the colorant may be used alone or in combination of two or more. In particular, two or more types are preferable from the viewpoint of uniformly shielding light in the visible region.
(A) Although the kind of pigment which can be used as a coloring agent is not specifically limited, For example, an organic pigment and an inorganic pigment are mentioned. Among these, it is preferable to use an organic pigment from the viewpoint of insulation and low dielectric constant.

Examples of organic pigments include organic black pigments and organic coloring pigments. Here, the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment, and a yellow pigment.
The chemical structure of the organic black pigment is not particularly limited, and examples thereof include lactam series, aniline series, perylene series, and cyanine series. Among these, a lactam organic black pigment is preferable from the viewpoint of light-shielding properties. The compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound An organic black pigment (hereinafter, sometimes abbreviated as “organic black pigment represented by the general formula (I)”) is more preferable. Since the organic black pigment represented by the general formula (I) has high absorbance in the visible light region, it tends to be able to form a colored partition wall having high light shielding properties.

In formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N = CH ₂ , N = CHR ¹¹ , N = CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
And at least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number. 2 to 12 alkynyl groups.

  The geometric isomer of the compound represented by the general formula (I) has the following core structure (however, the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable. .

  When the compound of general formula (I) is anionic, its charge can be any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal A salt compensated by a transition metal, a tertiary ammonium such as primary ammonium, secondary ammonium or trialkylammonium, a quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Further, when the geometric isomer of the compound represented by the general formula (I) is anionic, it is preferably a similar salt.

In the substituents of the general formula (I) and their definitions, the following is preferable because the shielding ratio tends to be high. This is because the following substituents are considered not to absorb and affect the hue of the pigment.
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom, a fluorine atom, or a chlorine atom, more preferably a hydrogen atom.
R ³ and R ⁸ are each independently preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH ₃ ) (C ₂ H ₅ ), N (C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^— , more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is the same, more preferably R ¹ is the same as R ⁶ , R ² is the same as R ⁷ , R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ Are the same.

  Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl Group, nonyl group, decyl group, undecyl group or dodecyl group.

  Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuzyl group, a norbornyl group, a bornyl group, and a norcaryl group. , Caryl group, menthyl group, norpinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.

  Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene. 2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, A 3-methyl-2-buten-1-yl group, a 1,4-pentadien-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group, or a dodecenyl group.

  Examples of the C3-C12 cycloalkenyl group include a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, and 2 , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4 (10) -tgen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -It is an yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.

  Examples of the alkynyl group having 2 to 12 carbon atoms include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl. Group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-in-1-yl Group, trans-3-methyl-2-penten-4-in-1-yl group, 1,3-hexadiin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decin-10-yl group or 1-dodecin-12-yl group.

  The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  The organic black pigment represented by the general formula (I) is preferably a compound represented by the following general formula (I-1).

Specific examples of such organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
This organic black pigment is preferably used after being dispersed by a dispersant, a solvent and a method described later. Moreover, when the sulfonic acid derivative of the general formula (I-1) is present during dispersion, dispersibility and storage stability may be improved.

  On the other hand, the colorant (a) may contain an organic coloring pigment, and may be used alone or in combination of two or more. In particular, when used for a light-shielding application, it is preferable to use a combination of organic coloring pigments having different colors, and it is more preferable to use a combination in which the displayed color is black.

  The chemical structure of the organic coloring pigment is not particularly limited, but various organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene are used. Inorganic pigments can also be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, 272, more preferably C.I. I. Pigment red 149, 177, 179, 209, 224, 254, 272.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Red 177, 254, and 272 are preferably used. When the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. From C.I. I. More preferably, CI pigment red 254 and 272 are used.

Examples of orange (orange) pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. Pigment orange 38, 43, 64, 71, 72.
In terms of dispersibility and light shielding properties, C.I. I. CI pigment oranges 43, 64, and 72 are preferably used. When the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. From C.I. I. More preferably, CI pigment oranges 64 and 72 are used.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, more preferably C.I. I. Pigment blue 15: 6, 16, 60.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used. When the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate, From this point of view, C.I. I. More preferably, CI Pigment Blue 60 is used. On the other hand, in order to increase the light shielding property, it is preferable to use a material having a high absorbance in the visible light region. I. More preferably, CI Pigment Blue 15: 6 is used.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, 29, more preferably C.I. I. And CI Pigment Violet 23 and 29.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Violet 23 and 29 are preferably used, and when the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate. C. I. More preferably, pigment violet 29 is used.

Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Among these pigments, it is preferable to use at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment and a purple pigment, and at least one selected from the group consisting of a red pigment and an orange pigment, and a blue pigment And at least one combination selected from the group consisting of purple pigments is more preferable. Thus, there exists a tendency which can achieve high light-shielding property by using the combination of a specific pigment.

Among these, from the viewpoint of light shielding properties and color tone, it is preferable to contain at least one of the following pigments.
Red pigment: Color index pigment red 177, 254, 272
Orange pigment: Color index pigment orange 43, 64, 72
Blue pigment: Color index pigment blue 15: 6, 60
Purple pigment: Color index pigment violet 23, 29

The combination of colors is not particularly limited, but from the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment, and a purple pigment can be mentioned. .
Among these, a combination of a blue pigment and an orange pigment is preferable because it tends to increase the light absorption in the visible region and improve the shielding rate while ensuring the light transmittance in the ultraviolet region.

In addition to these organic black pigments and organic color pigments, other black colorants can be used as other colorants.
As other black colorants, for example, inorganic black pigments can be used. Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like. Among these, carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics. Examples of carbon black include the following carbon black.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, PrintP85, PrintP85, PrintP85 U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBl4, ck FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (99, REGAL 99) REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark; the same shall apply hereinafter) XC72R, ELFTEX (registered trademark) -8
Made by Colombian Carbon: RAVEN (registered trademark; the same applies hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RA10850RA, RA10850RA, RA40850RA RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

  Carbon black coated with a resin may be used. Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance. As carbon black coated with resin, for example, carbon black described in JP-A No. 09-71733 can be suitably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

  As carbon black to be subjected to a coating treatment with a resin, the total content of Na and Ca is preferably 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe. The ash content of etc. is contained on the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electricity Tend to prevent mechanical short circuit.

  As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw oil, fuel oil (or gas) and reaction stop water when producing carbon black. This is possible by reducing the addition amount of the alkaline substance for adjusting the structure as much as possible. As another method, carbon black produced from the furnace is washed with water, hydrochloric acid or the like, and Na or Ca is dissolved and removed.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, carbon black moves to the solvent side and is completely separated from water when a solvent that is hardly soluble in water is added. At the same time, most of Na and Ca present in the carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there may be a case where a carbon black production process alone or a water or acid dissolution method alone with carefully selected raw materials may be possible. The total amount of Na and Ca can be easily made 100 ppm or less.

  The resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to cover fine units. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 ml / 100 g or less. By setting it within the above range, a coating film having good light shielding properties tends to be obtained. The average particle diameter means the number average particle diameter. Particle images are analyzed by taking several fields of photographs taken at tens of thousands of times by electron microscope observation, and measuring about 2000 to 3000 particles of these photographs with an image processing apparatus. This means the equivalent circle diameter obtained by.

  The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, After mixing and stirring a resin solution obtained by mixing a resin and a solvent such as cyclohexanone, toluene, xylene and the like, and a suspension obtained by mixing carbon black and water, carbon black and water are separated, 1. A method in which the composition obtained by removing water and heating and kneading is formed into a sheet, pulverized and then dried; A method in which the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate carbon black and the resin, and then the resulting granular material is separated and heated to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the above exemplified solvent, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and then a resin is added thereto. 3. dry blending method; A reactive group-containing monomer component constituting the resin to be coated and water are stirred at a high speed to prepare a suspension. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension. A method of adding carbon black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.

The type of resin to be coated is not particularly limited, but a synthetic resin is common, and a resin having a benzene ring in its structure has a stronger function as an amphoteric surfactant. From the viewpoints of stability and dispersion stability.
Specific synthetic resins include phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin and other thermosetting resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used. The coating amount of the resin with respect to the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and there is a tendency that the coating can be made sufficiently by setting the amount to the lower limit value or more. On the other hand, by setting it to the upper limit value or less, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.

  The carbon black coated with the resin in this way can be used as a light shielding material for the partition according to a conventional method, and an organic electroluminescence device having this partition as a constituent element can be prepared by a conventional method. When such carbon black is used, there is a tendency that it can be achieved at a high light shielding rate and at a low cost. Further, by coating the surface of carbon black with a resin, it is possible to create a partition with higher resistance and lower dielectric constant.

These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the standard of the average particle diameter is the number of pigment particles.
In the present invention, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering (DLS). The particle size measurement is performed by sufficiently diluting a colored photosensitive resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by a measuring instrument, According to its concentration) and measured at 25 ° C.

In addition to the above-described organic black pigment, organic color pigment, and other black colorants, a dye may be used. Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

<(B) Alkali-soluble resin>
The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group. For example, epoxy (meth) acrylate resin, acrylic resin, carboxyl group-containing epoxy resin, carboxyl group-containing urethane Resins, novolac resins, polyvinylphenol resins and the like can be mentioned, among which epoxy (meth) acrylate resins and acrylic resins are preferable. These can be used individually by 1 type or in mixture of multiple types.

  The epoxy (meth) acrylate resin is preferably a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin and further reacting with a polybasic acid or an anhydride thereof. For example, by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (—COO—). The thing which one carboxy group of the polybasic acid anhydride was added to the hydroxyl group produced in that case is mentioned. Moreover, when adding a polybasic acid anhydride, what was added by adding a polyhydric alcohol simultaneously is also mentioned.

Here, the epoxy resin includes the raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxyoxyfluorene type epoxy resin, dihydroxyalkyleneoxyl fluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4′-hydroxy) Phenyl) adamantane diglycidyl ether, and the like, and those having an aromatic ring in the main chain can be suitably used.

  Among them, from the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, 9,9-bis (4′-hydroxyphenyl) fluorene Diglycidyl etherified compounds are preferable, and bisphenol A epoxy resin is more preferable.

  Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adduct, penta Erythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydro Examples include phthalic anhydride adducts, reaction products of (meth) acrylic acid and ε-caprolactone. Among these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

  Examples of the polybasic acid (anhydride) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , Benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and anhydrides thereof. Among these, from the outgas viewpoint, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and succinic anhydride is preferable. More preferred are.

By using a polyhydric alcohol, the molecular weight of the epoxy (meth) acrylate resin can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity tend to be balanced. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency that balance of sensitivity, adhesion, etc. is easily obtained.
Examples of the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably there is.

  The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, still more preferably 60 mgKOH / g or more, 80 mgKOH / g The above is particularly preferable, 100 mgKOH / g or more is most preferable, 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less is more preferable, 130 mgKOH / g or less is more preferable, 120 mgKOH / g or less The following are particularly preferred: When the amount is not less than the lower limit value, the developability of the unexposed portion tends to be improved, and when the value is not more than the upper limit value, there is a tendency that a film that does not cause film reduction or the like can be generated.

  The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, particularly preferably 5000 or more, and usually 30000. Hereinafter, it is preferably 20000 or less, more preferably 15000 or less, further preferably 10,000 or less, and particularly preferably 8000 or less. By setting it to the lower limit value or more, there is a tendency that a film that does not cause film reduction or the like can be generated, and by setting the upper limit value or less, the developability of the unexposed area tends to be improved.

  The epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added to cause addition reaction, and further a polybasic acid or its A method of continuing the reaction by adding an anhydride can be used.

  Here, examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, and tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride. 1 type or 2 types or more, such as quaternary ammonium salts, phosphorus compounds, such as a triphenylphosphine, and stibines, such as a triphenylstibine, are mentioned. Furthermore, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

  The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to one chemical equivalent of the epoxy group of the epoxy resin. The amount can be. Moreover, as temperature at the time of addition reaction, it is 60-150 degreeC normally, Preferably it can be set as the temperature of 80-120 degreeC. Further, the polybasic acid (anhydride) is used in an amount of usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 based on 1 chemical equivalent of the hydroxyl group generated in the addition reaction. The amount can be a chemical equivalent.

The chemical structure of the epoxy (meth) acrylate resin is not particularly limited, but from the viewpoint of outgassing, an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (b1) and / or the following general formula (b2) It is preferable to contain the epoxy (meth) acrylate resin which has the partial structure represented by these. The epoxy (meth) acrylate resin has high sensitivity, and therefore has good patterning performance, has a hydrophobic skeleton, and has a mild dissolution rate, and thus has good substrate adhesion.
In particular, those having a repeating unit structure represented by the following general formula (b1) and / or those having a partial structure represented by the following general formula (b2) have a bulky and rigid skeleton at the center, It is considered that a hydrophilic portion such as a (meth) acryloyl group is developed outward and the developability is improved.

In the formula (b1), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (b1) may be further substituted with an arbitrary substituent. * Represents a bond.

In formula (b2), each R ²³ independently represents a hydrogen atom or a methyl group. R ²⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R ²⁵ and R ²⁶ each independently represents a divalent aliphatic group which may have a substituent. m and n each independently represents an integer of 0 to 2. * Represents a bond.

((B1) Epoxy (meth) acrylate resin)
Next, an epoxy (meth) acrylate resin having a repeating unit structure represented by the general formula (b1) (hereinafter abbreviated as “(b1) epoxy (meth) acrylate resin”) will be described in detail.

In the formula (b1), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (b1) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ²² )
In the formula (b1), R ²² represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group include an iso-propyl group, a sec-butyl group, a tert-butyl group, and an iso-amyl group.
The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 12 or less and 10 or less. When the amount is not less than the lower limit value, a strong film tends to be obtained and the substrate adhesion tends to be good. When the value is not more than the upper limit value, it is easy to suppress deterioration of the surface smoothness and sensitivity of the film, and resolution. Tend to improve. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom. And a group in which two are removed. Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.

  Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, amyl group, iso-amyl group and other alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. . Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.

  The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, naphthalene ring, anthracene having one free valence And groups such as a ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzoic ring having one free valence. Thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.

  Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoints of development solubility and moisture absorption resistance.

In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (b1-A) to (b1-E) Is mentioned. Among these, a group represented by the following formula (b1-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the film.

As described above, the benzene ring in formula (b1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.

  The repeating unit structure represented by the formula (b1) is preferably a repeating unit structure represented by the following formula (b1-1) from the viewpoint of simplicity of synthesis.

In formula (b1-1), R ²¹ and R ²² have the same meanings as those in formula (b1). R ^X represents a hydrogen atom or a polybasic acid residue. * Represents a bond. The benzene ring in formula (b1-1) may be further substituted with an arbitrary substituent.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, biphenyltetracarboxylic acid.

(B1) The repeating unit structure represented by the formula (b1-1) contained in one molecule of the epoxy (meth) acrylate resin may be one type or two or more types, for example, R ^X is a hydrogen atom. And R ^X may be a polybasic acid residue.

  Further, the number of repeating unit structures represented by the formula (b1) contained in one molecule of (b1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, 20 or less, more preferably 15 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.

  (B1) The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, particularly preferably 3000 or more, and 30000 or less. Preferably, 20000 or less is more preferable, 10,000 or less is more preferable, and 8000 or less is particularly preferable. There exists a tendency for the residual film rate of a coloring photosensitive resin composition to become favorable by setting it as the said lower limit or more, and there exists a tendency for resolution to become favorable by setting it as the said upper limit or less.

  (B1) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 40 mgKOH / g or more, and even more preferably 50 mgKOH / g or more. 80 mg KOH / g or more is particularly preferred, 200 mg KOH / g or less is preferred, 150 mg KOH / g or less is more preferred, 130 mg KOH / g or less is more preferred, and 110 mg KOH / g or less is particularly preferred. When the amount is not less than the above lower limit, the development solubility is improved and the resolution tends to be good, and when the amount is not more than the above upper limit, the remaining film ratio of the colored photosensitive resin composition becomes good. Tend.

  Specific examples of (b1) epoxy (meth) acrylate resin are given below.

((B2) Epoxy (meth) acrylate resin)
Next, an epoxy (meth) acrylate resin having a partial structure represented by the general formula (b2) (hereinafter abbreviated as “(b2) epoxy (meth) acrylate resin”) will be described in detail.

In formula (b2), each R ²³ independently represents a hydrogen atom or a methyl group. R ²⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R ²⁵ and R ²⁶ each independently represents a divalent aliphatic group which may have a substituent. m and n each independently represents an integer of 0 to 2. * Represents a bond.

(R ²⁴⁾
In the general formula (b2), R ²⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic ring group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, There is a tendency that the resolution is improved.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of the remaining film ratio and resolution of the colored photosensitive resin composition.

On the other hand, the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and more preferably 4 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, There is a tendency that the resolution is improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, it is more preferably 20 or less, and particularly preferably 15 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Examples include fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.

  Further, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, one or more And a group in which one or more divalent aromatic ring groups are linked to each other.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 25 or less, more preferably 20 or less, and even more preferably 15 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group include an iso-propyl group, a sec-butyl group, a tert-butyl group, and an iso-amyl group. Among these, a tert-butyl group is preferable from the viewpoint of the rigidity of the skeleton.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less, 5 or less, more preferably 3 or less. By setting the lower limit value or more, a strong film tends to be obtained and the substrate adhesion tends to be good, and by setting the upper limit value or less, it is easy to suppress the deterioration of the surface smoothness and sensitivity of the film, and the resolution. Tend to improve. Specific examples of the divalent aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms. Group. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.

  Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, amyl group, iso-amyl group and other alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. . Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.

  The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene And groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzoic ring having one free valence. Thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring is preferable, and a fluorene ring is more preferable.

  Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of development solubility.

In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (b1-A) to (b1-E) Is mentioned. Among these, the group represented by the formula (b1-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the film.

  The bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And a mode in which a cyclic hydrocarbon group which is a side chain including one of the carbon atoms of the aliphatic group is formed.

(R ^{25, 26} )
In the general formula (b2), R ²⁵ and R ²⁶ each independently represents a divalent aliphatic group which may have a substituent.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group include an iso-propyl group, a sec-butyl group, a tert-butyl group, and an iso-amyl group.
The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 12 or less and 10 or less. When the amount is not less than the lower limit value, a strong film tends to be obtained and the substrate adhesion tends to be good. When the value is not more than the upper limit value, it is easy to suppress deterioration of the surface smoothness and sensitivity of the film, and resolution. Tend to improve. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom. And a group in which two are removed. Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.

  Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, amyl group, iso-amyl group and other alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. . Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

(M, n)
In the said general formula (b2), m and n represent the integer of 0-2. When it is at least the lower limit, patterning suitability is good and surface roughness tends to be less likely to occur, and when it is at most the upper limit, developability tends to be good. M and n are preferably 0 from the viewpoint of developability, and m and n are preferably 1 or more from the viewpoint of patterning suitability and surface roughness.

  Moreover, it is preferable that the partial structure represented by the said general formula (b2) is a partial structure represented by the following general formula (b2-1) from a viewpoint of the adhesiveness to a board | substrate.

In the formula (b2-1), R ²³ , R ²⁵ , R ²⁶ , m and n are as defined in the formula (b2). R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. p is an integer of 1 or more. The benzene ring in formula (b2-1) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ^α )
In the general formula (b2-1), R ^α represents a monovalent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of strong film characteristics.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of development solubility.

  Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, C1-C5 alkyl groups, such as an amyl group and an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; A cyano group; A carboxyl group etc. are mentioned. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  p represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for a film hardening degree and a residual film rate to become favorable, and there exists a tendency for developability to become favorable by setting it as the said upper limit or less.

Among these, from the viewpoint of a strong film curing degree, R ^α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

As described above, the benzene ring in formula (b2-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.

  Specific examples of the partial structure represented by the formula (b2-1) are given below.

  The partial structure represented by the general formula (b2) is preferably a partial structure represented by the following general formula (b2-2) from the viewpoints of skeleton rigidity and membrane hydrophobization.

In the formula (b2-2), R ²³ , R ²⁵ , R ²⁶ , m and n are as defined in the formula (b2). ^Rβ represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (b2-2) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ^β )
In the formula (b2-2), the R ^beta, a divalent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic ring group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
Moreover, carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable. When the amount is not less than the above lower limit value, there is a tendency to suppress film deterioration during development, and when the amount is not more than the above upper limit value, it is easy to suppress the surface smoothness and sensitivity of the film, and the resolution is improved. Tend to be.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of storage stability.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 10 The above is more preferable, 40 or less is preferable, 30 or less is more preferable, 20 or less is further preferable, and 15 or less is particularly preferable. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of developability.

  Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, C1-C5 alkyl groups, such as an amyl group and an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; A cyano group; A carboxyl group etc. are mentioned. Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.

Among these, from the viewpoint of storage stability and electrical properties, it is preferred that R ^beta is a divalent aliphatic cyclic group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of low hygroscopicity and patterning properties of the coating film, it is preferred that R ^beta is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

As described above, the benzene ring in formula (b2-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics. Moreover, it is preferable that it is methyl group substitution from a viewpoint of making it hard to produce film reduction.

  Specific examples of the partial structure represented by the formula (b2-2) are given below.

  On the other hand, the partial structure represented by the formula (b2) is preferably a partial structure represented by the following formula (b2-3) from the viewpoint of the remaining film ratio and patterning characteristics.

In the formula (b2-3), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , m and n are as defined in the formula (b2). R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Further, another OH group may be removed and shared with R ^Z in the other molecule represented by the formula (b2-3), that is, a plurality of formulas (b2-3 are bonded via R ^Z. ) May be linked.
Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, biphenyltetracarboxylic acid.

(B2) The partial structure represented by the formula (b2-3) contained in one molecule of the epoxy (meth) acrylate resin may be one type or two or more types. For example, R ^Z is a hydrogen atom. , R ^Z may be a mixture of polybasic acid residues.

  The number of partial structures represented by the formula (b2) contained in one molecule of (b2) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable. By setting the lower limit value or more, it is easy to obtain a strong film, surface roughness is less likely to occur, and the electric characteristics tend to be good, and by setting the upper limit value or less, the surface smoothness and sensitivity of the film are reduced. Deterioration is easy to suppress and the resolution tends to improve.

  (B2) The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, particularly preferably 3500 or more, and 30000 or less. Preferably, 20000 or less is more preferable, 15000 or less is further preferable, 12000 or less is more preferable, and 10,000 or less is particularly preferable. When it is at least the lower limit value, the patterning characteristics tend to be good, and when it is at most the upper limit value, a strong film is likely to be obtained and surface roughness tends not to occur.

  (B2) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 40 mgKOH / g or more, still more preferably 60 mgKOH / g or more, 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 170 mgKOH / g or less is more preferable, and 150 mgKOH / g or less is more preferable. When the amount is not less than the lower limit, a strong film tends to be easily obtained, and when the amount is not more than the upper limit, the development solubility is improved and the resolution tends to be good.

  The epoxy (meth) acrylate resin may be used in combination with other alkali-soluble resins, and can be selected from resins usually used in colored photosensitive resin compositions. Examples thereof include binder resins described in JP 2007-271727 A, JP 2007-316620 A, JP 2007-334290 A, and the like. Any of these may be used alone or in combination of two or more.

  Further, as the (b) alkali-soluble resin, it is preferable to use an acrylic resin from the viewpoint of plate-making property, and those described in JP-A-2014-137466 can be preferably used.

Examples of the acrylic resin include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b1)”) and other copolymerizable ethylenically unsaturated monomers. Examples thereof include a copolymer with a monomer (hereinafter referred to as “unsaturated monomer (b2)”).
Examples of the unsaturated monomer (b1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacone Acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or anhydrides thereof; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as acryloyloxyethyl]; having carboxy groups and hydroxyl groups at both ends such as ω-carboxypolycaprolactone mono (meth) acrylate Polymer mono (meth) acrylate; p-vinylbenzoic acid and the like can be mentioned.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

  Examples of the unsaturated monomer (b2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α- Aromatic vinyl compounds such as methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane A macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, and the like.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) within such a range, a colored photosensitive resin composition excellent in alkali developability and storage stability tends to be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.
The copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) can be produced by a known method. For example, JP 2003-222717 A, JP 2006-259680 A The structure, Mw, and Mw / Mn can also be controlled by the method disclosed in Japanese Patent Publication No. 2007/029871.

<(C) Photopolymerization initiator>
The photopolymerization initiator (c) in the colored photosensitive resin composition of the present invention undergoes photocleavage and generates radicals in the exposure step. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazoles described in JP-A-2000-56118. Derivatives: Halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts described in JP-A-10-39503, N -Radical activators such as aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, and the like.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclo Tantadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl)
Examples include -4,6-bis (trichloromethyl) -s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is.

As the photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate-making property, and when using an alkali-soluble resin containing a phenolic hydroxyl group, it is disadvantageous in terms of sensitivity. Such an oxime ester compound having excellent sensitivity is useful.
Examples of the oxime ester-based compound include those described in International Publication No. 2008/077554, those described in International Publication No. 2009/131189, those described in JP 2011-132215 A, and International Publication No. Examples described in the pamphlet of 2008/078678 and those described in JP-T-2014-500852 can be mentioned.
The chemical structure of the oxime ester compound is not particularly limited, but a compound represented by the following general formula (II) is preferable from the viewpoint of sensitivity.

In the formula (II), R ³³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ³⁴ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1;
R ³⁵ represents -CO- (R ^39), - represents a O- (R ^40), or a nitro group. R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, a cyano group or a nitro group. q represents an integer of 0 to 4.
X represents —N (R ³⁶ ) — or —C (R ³⁷ ) (R ³⁸ ) —.
R ^{36 to} R ³⁸ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ³⁷ and R ³⁸ may be bonded to each other to form a ring.

( ^R33 )
In the formula (II), R ³³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
^Examples of the alkyl group for R ³³ include a linear, branched, or cyclic alkyl group. The number of carbon atoms is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 3 or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable from the viewpoint of sensitivity.
Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, and an amide group. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. On the other hand, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ³³ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, further preferably 8 or less, usually 4 or more, and preferably 6 or more. By setting it to the upper limit value or less, sensitivity tends to be improved, and by setting the upper limit value or more, synthesis tends to be facilitated.

  An aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring of the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene. And a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, and the like.

  An aromatic heterocyclic group means an aromatic heterocyclic ring having one free atomization. The aromatic heterocyclic ring of the aromatic heterocyclic group may be a single ring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring. Oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, Benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene And the like.

  Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a halogenoalkyl group (an alkyl group in which some or all of the hydrogen atoms are substituted with a halogen atom), halogeno Examples thereof include an alkoxy group (an alkoxy group in which some or all of the hydrogen atoms are substituted with halogen atoms), and an alkyl group is preferred from the viewpoint of ease of synthesis.

Among these, from the viewpoint of sensitivity, R ³³ is more preferably an unsubstituted alkyl group, and further preferably a methyl group.

(R ³⁴ )
In the formula (II), R ³⁴ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
^Examples of the alkyl group for R ³⁴ include linear, branched or cyclic alkyl groups. The carbon number is not particularly limited, but is preferably 1 or more from the viewpoint of solubility in the colored photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 20 or less, more preferably 18 or less, further preferably 15 or less, still more preferably 12 or less, and particularly preferably 11 or less. preferable.

Specific examples of the alkyl group include a methyl group, a hexyl group, and a cyclopentylmethyl group. Among these, a methyl group or a hexyl group is preferable, and a methyl group is more preferable from the viewpoint of developability.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and the like, and a hydroxyl group and a carboxyl group are preferable from the viewpoint of alkali developability. A carboxyl group is more preferred. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ³⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and combinations thereof. A carboxyl group is preferable, and a carboxyl group is more preferable.
Among these, from the viewpoint of developability, R ³⁴ is preferably an aromatic ring group which may have a substituent, and more preferably a phenyl group which may have a substituent.

(P)
In the formula (II), p represents 0 or 1. From the viewpoint of shortening the absorption spectrum, p is preferably 0, while from the viewpoint of photobleaching property, p is preferably 1.

(R ³⁵ )
In the formula (II), R ³⁵ represents —CO— (R ³⁹ ), —O— (R ⁴⁰ ) or a nitro group. R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, a cyano group or a nitro group. By thus R ³⁵ has an electron withdrawing believed sensitivity is improved. Among these, a nitro group is preferable from the viewpoint of sensitivity.

(R ³⁹ and R ⁴⁰⁾
R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, a cyano group or a nitro group.
Examples of the alkyl group for R ³⁹ and R ⁴⁰ include a linear, branched or cyclic alkyl group. The number of carbon atoms is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity, and more preferably 2 or more. Further, from the viewpoint of ease of synthesis, it is preferably 30 or less, more preferably 25 or less, further preferably 20 or less, still more preferably 15 or less, and preferably 15 or less. Particularly preferred.
Specific examples of the alkyl group include a methyl group, a hexyl group, and a cyclopentylmethyl group. Among these, a methyl group or a hexyl group is preferable, and a methyl group is more preferable from the viewpoint of sensitivity.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group, and an aromatic ring group and a hydroxyl group are preferable from the viewpoint of sensitivity. An aromatic ring group is more preferable. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ³⁹ and R ⁴⁰ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 6 or more from the viewpoint of sensitivity. Moreover, it is preferable that it is 18 or less from a viewpoint of synthetic | combination ease, It is more preferable that it is 14 or less, It is further more preferable that it is 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a thiophene group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of sensitivity.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of sensitivity, a hydroxyl group and an alkyl group are preferable. Is more preferable.
Among these, from the viewpoint of sensitivity, a phenyl group having an alkyl group is preferable, and among them, a phenyl group having a methyl group is particularly preferable.

(Q)
In said formula (II), q represents the integer of 0-4. Among these, q is preferably 1 from the viewpoint of sensitivity, and q is preferably 0 from the viewpoint of ease of synthesis.

(X)
In the formula (II), X represents —N (R ³⁶ ) — or —C (R ³⁷ ) (R ³⁸ ) —. From the viewpoint of sensitivity, X is preferably —N (R ³⁶ ) —, while from the viewpoint of ease of synthesis, X is preferably —C (R ³⁷ ) (R ³⁸ ) —.

(R ³⁶ ~R ³⁸⁾
In the formula (II), R ^{36 to} R ³⁸ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ³⁷ and R ³⁸ may be bonded to each other to form a ring.

Examples of the alkyl group for R ^{36 to} R ³⁸ include a linear, branched or cyclic alkyl group. The number of carbon atoms is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity, and more preferably 2 or more. Further, from the viewpoint of ease of synthesis, it is preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 4 or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclopentylmethyl group. Among these, from the viewpoint of sensitivity, an ethyl group or a butyl group is preferable, and an ethyl group is preferable. More preferred.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group, and an aromatic ring group and a hydroxyl group are preferable from the viewpoint of sensitivity. An aromatic ring group is more preferable. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group in R ^{36 to} R ³⁸ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 6 or more from the viewpoint of sensitivity. Moreover, it is preferable that it is 18 or less from a viewpoint of synthetic | combination ease, It is more preferable that it is 14 or less, It is further more preferable that it is 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of sensitivity.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of sensitivity, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is preferable. More preferred. Further, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
Among these, from the viewpoint of developability, R ^{36 to} R ³⁸ are preferably each independently an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and an ethyl group More preferably.

On the other hand, examples of the ring formed by bonding R ³⁷ and R ³⁸ to each other include the following structures.

  Specific examples of the oxime ester compound include the following.

  Although it does not specifically limit about the manufacturing method of the oxime ester type compound represented by the said general formula (II), For example, it can manufacture by the method of Unexamined-Japanese-Patent No. 2000-080068.

A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
A sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity. As sensitizing dyes, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, JP-A 54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-10776 -210240 discloses, can be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethyl) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

  Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. It is done. A polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.

<(D) Photopolymerizable compound>
The colored photosensitive resin composition of the present invention contains (d) a photopolymerizable compound. (D) It is thought that it becomes high sensitivity by including a photopolymerizable compound.
The photopolymerizable compound used in the present invention is not particularly limited as long as it is a compound that is polymerized by light irradiation, and examples thereof include compounds having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 3 or more, more preferably 5 or more, and preferably 15 or less. More preferably, it is 10 or less. By setting it as the said lower limit or more, there exists a tendency for polymerizability to improve and to become high sensitivity, and there exists a tendency for developability to become more favorable by setting it as the said upper limit or less.
Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound. Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (made by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (made by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical).

Among these, from the viewpoint of sensitivity, it is preferable to use ester (meth) acrylates or urethane (meth) acrylates as the ethylenically unsaturated compound, and to use a dipentaerythritol hexaacrylate dimer. More preferred.
These may be used alone or in combination of two or more.

<(E) Solvent>
The colored photosensitive resin composition of the present invention contains (e) a solvent. (E) By containing a solvent, (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound or the like is dissolved or dispersed, and the viscosity is adjusted. Can have.
The colored photosensitive resin composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (d) a photopolymerizable compound, (f) a dispersant, and other types used as necessary. Various materials are used in a state of being dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferable from the viewpoints of solubility and dispersibility.

  Among organic solvents, those having a boiling point in the range of 100 to 300 ° C. are preferably selected from the viewpoint of dispersibility and coating properties, and those having a boiling point in the range of 120 to 280 ° C. are more preferable. The boiling point here means the boiling point at a pressure of 1013.25 hPa.

Examples of such organic solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.

Commercially available organic solvents corresponding to the above include mineral spirits, Valsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cerosolve” is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name).
These organic solvents may be used alone or in combination of two or more.

  When forming a black matrix or a colored spacer by photolithography, an organic solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 hPa, the same applies to the boiling point hereinafter) is selected. Is preferred. More preferably, it has a boiling point of 120 to 170 ° C.

Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. In addition, glycol monoalkyl ethers are highly polar, and if the addition amount is too large, the pigment is likely to aggregate, and the storage stability such as the viscosity of the colored photosensitive resin composition obtained later tends to decrease. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, the colored photosensitive resin composition is difficult to dry, but has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. . That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it to the lower limit value or more, for example, there is a tendency to suppress the occurrence of foreign matter defects due to precipitation and solidification of color materials at the tip of the slit nozzle, and by setting the lower limit value or less, the drying temperature of the composition Tends to be able to suppress slowing down and to prevent problems such as tact failure in the vacuum drying process and pre-baked pin marks

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

<(F) Dispersant>
In the colored photosensitive resin composition of the present invention, (a) it is important to finely disperse the colorant and stabilize the dispersion state, so that it is important to ensure the stability of the quality. Including.
Further, the dispersant (f) contained in the colored photosensitive resin composition of the present invention contains an acidic group and a basic group. In this way, by using a dispersant containing an acidic group and a basic group, the polymer complex can be formed by the electrostatic interaction between the acidic group and the basic group and the van der Waals force between the parent solvent groups. It is thought to form. By coordinating the basic ions of the developer to the acidic groups on the surface of the polymer complex, the polymer complex is dissolved or dispersed in the developer, and the dispersant on the substrate surface is completely removed in the development process, resulting in organic electroluminescence. It is considered that generation of a non-light emitting region of the element is eliminated.

Examples of such an acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, a phosphoric acid group and a sulfonic acid group are preferable from the viewpoint of valence, and a phosphoric acid group is more preferable. From the viewpoint of dispersibility, a carboxyl group and a phosphate group are preferable, and a phosphate group is more preferable. Moreover, a carboxyl group and a phosphoric acid group are preferable from a compatible viewpoint with alkali-soluble resin, and a carboxyl group is more preferable.
Examples of basic groups include primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, pyrazine and imidazole. Among these, a tertiary amino group or a quaternary ammonium base is preferable from the viewpoint of dispersibility.
Moreover, as a dispersing agent, what has both an acidic group and a basic group in the same molecule | numerator may be used, and 2 or more types of dispersing agents which have any functional group may be mixed and used. .

The chemical structure of the dispersant is not particularly limited, and examples thereof include those having a compatible chain that is compatible with a pigment adsorbing group that adsorbs to a pigment and a resin or the like for forming a steric hindrance.
Examples of the pigment adsorbing group include the aforementioned acidic group and basic group. On the other hand, the compatible chain is not particularly limited as long as it is oriented to a resin or the like, and examples thereof include an alkyl chain, a polyether chain, and a polyester chain.

  (F) Although the weight average molecular weight of a dispersing agent is not specifically limited, 1000 or more are preferable, 2000 or more are more preferable, 3000 or more are more preferable, 4000 or more are especially preferable, 1000000 or less are preferable, and 100000 or less are more preferable. 50000 or less is more preferable, and 20000 or less is particularly preferable. Dispersibility tends to be improved by setting it to the lower limit value or more, and dispersibility tends to be improved by setting the upper limit value or less. (F) The molecular weight of the dispersing agent means the molecular weight of the dispersing agent when there is one dispersing agent, and the weighted average according to the content ratio (mass ratio) when the dispersing agent is a mixture of two or more dispersing agents. It means a numerical value obtained by taking

  (F) The acid value of the dispersant is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, further preferably 5 mgKOH / g or more, particularly preferably 10 mgKOH / g or more, and 200 mgKOH / g. The following is preferable, 180 mgKOH / g or less is more preferable, 160 mgKOH / g or less is further preferable, and 140 mgKOH / g or less is particularly preferable. By setting it to the lower limit value or more, there is a tendency to suppress the generation of a non-light emitting portion region of the light emitting portion of the organic electroluminescent element, and dispersibility tends to be improved by setting the upper limit value or less. (F) The acid value of the dispersant means the acid value of the dispersant when there is one dispersant, and depending on the content ratio (mass ratio) when the dispersant is a mixture of two or more. It means a numerical value obtained by taking a weighted average.

  (F) The amine value of the dispersant is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, further preferably 5 mgKOH / g or more, particularly preferably 10 mgKOH / g or more, and 200 mgKOH / g. The following is preferable, 180 mgKOH / g or less is more preferable, 160 mgKOH / g or less is further preferable, and 140 mgKOH / g or less is particularly preferable. Dispersibility tends to be improved by setting it to the lower limit value or more, and there is a tendency to suppress generation of a non-light emitting portion region of the light emitting portion of the organic electroluminescent element by setting the upper limit value or less. (F) The amine value of the dispersant means the amine value of the dispersant when the dispersant is one type, and according to the content ratio (mass ratio) when the dispersant is a mixture of two or more types. It means a numerical value obtained by taking a weighted average.

  Examples of the dispersant include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), and SOLPERSE. (Registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Azisper (registered trademark, manufactured by Ajinomoto Co., Inc.), TEGO DISPER (registered trademark, manufactured by Evonik). Etc.
These dispersing agents may be used individually by 1 type, or may use 2 or more types together.

  Among these, as the dispersant having an acidic group, a phosphoric acid compound is preferable from the viewpoint of suppressing generation of a non-light emitting region in the vicinity of the partition wall of the light emitting portion.

  Although the specific structure of the phosphoric acid compound is not particularly limited, a compound represented by the following formula (X1) is preferable from the viewpoint of dispersibility.

In the formula (X1), R ⁴¹ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a monovalent group represented by the following formula (X2). . k represents an integer of 1 to 3, and δ represents a direct bond or a divalent linking group.

In the formula (X2), R ⁴² represents an alkyl group which may have a substituent, and R ⁴³ represents an alkylene group which may have a substituent. l represents an integer of 0 to 15. When l is an integer of 2 or more, the plurality of R ⁴³ contained in the formula may be the same or different. * Represents a bond.

(R ⁴¹ )
In the formula (X1), R ⁴¹ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a monovalent group represented by the following formula (X2). .
The number of carbon atoms of the alkyl group in R ⁴¹ is not particularly limited, but is usually 1 or more, usually 8 or less, preferably 6 or less, more preferably 4 or less, further preferably 2 or less, and particularly preferably 1. is there. There exists a tendency for a dispersibility to become favorable by setting it as the said upper limit or less.

  The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. Among these, from the viewpoint of affinity for a solvent, a methyl group An ethyl group is preferable, and a methyl group is more preferable.

The number of carbon atoms of the alkenyl group in R ⁴¹ is not particularly limited, but is usually 2 or more, usually 8 or less, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. There exists a tendency for a dispersibility to become favorable by setting it as the said upper limit or less.
The alkenyl group may be linear or branched. Specific examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, and an isopropenyl group.

Examples of the substituent that the alkyl group or alkenyl group in R ⁴¹ may have include an aryl group, a cycloalkyl group, and a halogen atom. Among these, unsubstituted is preferable from the viewpoint of affinity for the solvent.

As described above, R ⁴¹ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a monovalent group represented by the following formula (X2). Among these, a monovalent group represented by the formula (X2) is preferable from the viewpoint of affinity for a solvent.

( ^R42 )
Wherein (X2), R ⁴² represents an alkyl group which may have a substituent.
The number of carbon atoms of the alkyl group in R ⁴² is not particularly limited, but is usually 1 or more, usually 8 or less, preferably 6 or less, more preferably 4 or less, still more preferably 2 or less, and particularly preferably 1. There exists a tendency for a dispersibility to become favorable by setting it as the said upper limit or less.

  The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. From the viewpoint of affinity for a solvent, a methyl group and an ethyl group are preferable. Preferably, a methyl group is more preferable.

Examples of the substituent that the alkyl group for R ⁴² may have include an aryl group, a cycloalkyl group, and a halogen atom. Among these, unsubstituted is preferable from the viewpoint of affinity for the solvent.

(R ⁴³ )
In formula (X2), R ⁴³ represents an alkylene group which may have a substituent.
The number of carbon atoms of the alkylene group in R ⁴³ is not particularly limited, but is usually 2 or more, usually 4 or less, preferably 3 or less. There exists a tendency for a dispersibility to become favorable by setting it as the said upper limit or less.

  The alkylene group may be linear or branched. Specific examples of the alkylene group include an ethylene group, a propylene group, an iso-propylene group, an n-butylene group, and an iso-butylene group. From the viewpoint of affinity for a solvent, an ethylene group, an iso-propylene group, an n- A butylene group is preferred, and an ethylene group is more preferred.

Examples of the substituent that the alkylene group for R ⁴³ may have include an aryl group, a cycloalkyl group, and a halogen atom. Among these, unsubstituted is preferable from the viewpoint of affinity for the solvent.

(L)
In the formula (X2), l represents an integer of 0 to 15, preferably 1 or more, more preferably 5 or more, still more preferably 8 or more, and preferably 12 or less, more preferably 10 or less. There exists a tendency for the affinity with respect to a solvent to become favorable by setting it as the said lower limit or more, and there exists a tendency for the affinity with respect to a pigment to become favorable by setting it as the said upper limit or less.

(K)
In formula (X1), k represents an integer of 1 to 3, but 1 is preferable from the viewpoint of affinity for the pigment.

(Δ)
In the formula (X1), δ represents a direct bond or a divalent linking group, and among them, a divalent linking group represented by the following formula (X3) is preferable from the viewpoint of affinity for a solvent.

In formula (X3), R ⁴⁴ and R ⁴⁵ each independently represents an alkylene group which may have a substituent. m and n each independently represents an integer of 0 to 10. * Represents a bond.

( ^R44 and ^R45 )
In formula (X3), R ⁴⁴ and R ⁴⁵ each independently represents an alkylene group which may have a substituent.
The number of carbon atoms of the alkylene group in R ⁴⁴ and R ⁵⁵ is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and particularly preferably 5 or more. Moreover, it is 10 or less normally, Preferably it is 7 or less, More preferably, it is 6 or less, More preferably, it is 5 or less. When the amount is not less than the lower limit, there is a tendency that a change with time after dispersion tends to be small, and when the amount is not more than the upper limit, the dispersibility tends to be good.
The alkylene group may be linear or branched. Specific examples of the alkylene group include methylene group, ethylene group, n-propylene group, iso-propylene group, n-butylene group, iso-butylene group, n-pentyl group, n-hexyl group, and n-heptyl group. And n-butylene group, iso-butylene group, n-pentyl group and n-hexyl group are preferable from the viewpoint of affinity with a solvent, and n-butylene group and n-pentyl group are more preferable.
Examples of the substituent that the alkylene group may have include an aryl group, a cycloalkyl group, and a halogen atom. Among these, unsubstituted is preferable from the viewpoint of affinity with a solvent.

(M and n)
In formula (X3), m and n each independently represents an integer of 0 to 10. Among these, Preferably it is 1 or more, More preferably, it is 2 or more, More preferably, it is 3 or more, Preferably it is 8 or less, More preferably, it is 5 or less, More preferably, it is 4 or less. There exists a tendency for the affinity with respect to a solvent to become favorable by setting it as the said lower limit or more, and there exists a tendency for the affinity with respect to a pigment to become favorable by setting it as the said upper limit or less.

  Among the compounds represented by the formula (X1), a compound represented by the following formula (X4) is more preferable from the viewpoint of affinity with a solvent.

In formula (X4), R ^{42 to} R ⁴⁵ , k, l, m, and n are as defined in formula (X1).

  The weight average molecular weight of the dispersant having an acidic group is not particularly limited, but is preferably 500 or more, more preferably 800 or more, further preferably 1000 or more, more preferably 50000 or less, more preferably 10,000 or less, and even more preferably 5000 or less. Preferably, 2000 or less is especially preferable. There exists a tendency for affinity with a solvent to improve by setting it as the said lower limit or more, and there exists a tendency for affinity with a pigment to improve by setting it as the said upper limit or less.

  The acid value of the dispersant having an acidic group is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, further preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, and 40 mgKOH / g or more. Is particularly preferable, 80 mgKOH / g or more is most preferable, 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 160 mgKOH / g or less is more preferable, and 140 mgKOH / g or less is particularly preferable. By setting it to the lower limit value or more, there is a tendency to suppress the generation of a non-light emitting portion region of the light emitting portion of the organic electroluminescent element, and dispersibility tends to be improved by setting the upper limit value or less.

  As the dispersant having a basic group, a dispersant having a basic group such as an amino group or an ammonium base is preferable. Among these basic groups, a tertiary amino group or a quaternary ammonium base is preferable from the viewpoint of dispersibility.

  Among the dispersants having a basic group, a low molecular weight amine compound is preferable, and a compound represented by the following formula (X5) is more preferable from the viewpoint that the effect as a dispersant is generated in a small amount.

In formula (X5), R ⁴⁶ represents an alkyl group which may have a substituent, and R ⁴⁷ represents an alkylene group which may have a substituent. Two R ⁴⁶ contained in the formula (X5) may be the same or different.

(R ⁴⁶ )
In the formula (X5), R ⁴⁶ represents an alkyl group which may have a substituent.
The number of carbon atoms of the alkyl group in R ⁴⁶ is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and usually 6 or less, preferably 5 or less, more preferably 4 or less. When the amount is not less than the lower limit, there is a tendency that a change with time after dispersion does not easily occur, and when the amount is not more than the upper limit, the dispersibility tends to be good.

  The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. Among these, from the viewpoint of a change with time after dispersion, n -Propyl group and n-butyl group are preferable, and n-butyl group is more preferable.

Examples of the substituent that the alkyl group for R ⁴⁶ may have include an aryl group, a cycloalkyl group, and a halogen atom. Among these, unsubstituted is preferable from the viewpoint of affinity for the solvent.

(R ⁴⁷ )
In the formula (X5), R ⁴⁷ represents an alkylene group which may have a substituent.
The number of carbon atoms of the alkylene group in R ⁴⁷ is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less. When the amount is not less than the lower limit, there is a tendency that a change with time after dispersion does not easily occur, and when the amount is not more than the upper limit, the dispersibility tends to be good.

  The alkylene group may be linear or branched. Specific examples of the alkylene group include an ethylene group, a propylene group, an iso-propylene group, an n-butylene group, and an iso-butylene group. From the viewpoint of dispersibility, an ethylene group, an iso-propylene group, and an n-butylene group. Are preferable, and an ethylene group is more preferable.

Examples of the substituent that the alkylene group for R ⁴⁷ may have include an aryl group, a cycloalkyl group, and a halogen atom. Among these, unsubstituted is preferable from the viewpoint of dispersibility.

On the other hand, from the viewpoint of dispersion stability, it is preferable to include a polymer dispersant having a basic group, more preferably to include a urethane polymer dispersant and / or an acrylic polymer dispersant. It is particularly preferred to include a molecular dispersant.
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic group and further having a polyester bond and / or a polyether bond is preferable.

Examples of the urethane-based and acrylic polymer dispersant include DISPERBYK160 to 167, 182 series (all are urethane-based), DISPERBYK2000, LPN21116 and the like (all are acrylic-based) (all manufactured by BYK Chemie).
If a chemical structure preferable as a urethane polymer dispersant is specifically exemplified, for example, the same as a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamine such as methyldiethanolamine) obtained by polycondensation such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the above diols or carbon number 1 ~ 25 monovalent a Polylactone diol or polylactone monool obtained by using the call as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
These may be used alone or in combination of two or more.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero 6-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.
These may be used alone or in combination of two or more.

  The preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. To 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3. -24 parts by mass.

  The production of the urethane-based polymer dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned. These may be used alone or in combination of two or more.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

  In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.

  On the other hand, as an acrylic polymer dispersant, a random copolymer of an unsaturated group-containing monomer having a basic group and an unsaturated group-containing monomer having no basic group, graft copolymer It is preferable to use a polymer or a block copolymer. These copolymers can be produced by a known method.

  As unsaturated group-containing monomers having basic groups, unsaturated monomers having tertiary amino groups and quaternary ammonium bases such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof. A monomer is mentioned as a specific example. These may be used alone or in combination of two or more.

  Unsaturated group-containing monomers having no basic group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclo N-substituted maleimides such as xylmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. These may be used alone or in combination of two or more.

  The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a basic group and a B block having no basic group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the basic group, the A block contains a partial structure derived from the unsaturated group-containing monomer not containing the basic group. These may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, content in the A block of the partial structure which does not contain a functional group is 80 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less.

The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the basic group, but one B block contains partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are each an integer of 1 or more.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are each an integer of 1 or more, and R ^a is a hydrogen atom or 1 R ^b is ^a hydrogen atom different from R ^a or a monovalent organic group.

  In synthesizing this acrylic polymer dispersant, JP-A-9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W.H. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.

The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a B-A-B block copolymer, and the A block constituting the copolymer. The / B block ratio is preferably 1/99 to 80/20, particularly preferably 5/95 to 60/40 (mass ratio), and within this range tends to ensure good heat resistance and dispersion stability. There is.
Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol, There exists a tendency which can ensure favorable heat resistance and dispersion stability by making it in the range.

  The molecular weight of the dispersant having a basic group is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, particularly preferably 4000 or more, preferably 1000000 or less, more preferably 100000 or less. 50000 or less is more preferable, and 20000 or less is particularly preferable. Dispersibility tends to be improved by setting it to the lower limit value or more, and dispersibility tends to be improved by setting the upper limit value or less.

The amine value of the dispersant having a basic group is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 50 mgKOH / g or more, more preferably 90 mgKOH / g or less, 80 mgKOH / g g or less is more preferable, and 75 mgKOH / g or less is more preferable. When the amount is not less than the lower limit value, the dispersibility tends to be good, and when the value is not more than the upper limit value, there is a tendency that a change with time after dispersion is small.
Here, the amine value of the dispersant having a basic group is represented by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]

  In the case of having a quaternary ammonium base as a basic group, the specific structure of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as “repeating unit”) , “Sometimes referred to as“ repeat unit (i) ”).

In the above formula (i), R ^{31 to} R ³³ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aralkyl group that may be present, and two or more of R ^{31 to} R ³³ may be bonded to each other to form a cyclic structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group, and Y ⁻ is a counter anion.

The carbon number of the alkyl group which may have a substituent in R ^{31 to} R ³³ in the above formula (i) is not particularly limited, but is usually 1 or more and preferably 10 or less. The following is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ^{31 to} R ³³ in the above formula (i) is not particularly limited, but is usually 6 or more and preferably 16 or less. The following is more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, a phenyl group, a methylphenyl group, and an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in R ^{31 to} R ³³ in the above formula (i) is not particularly limited, but is usually 7 or more and preferably 16 or less. The following is more preferable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoint of dispersibility, R ^{31 to} R ³³ are preferably each independently an alkyl group or an aralkyl group. Specifically, R ³¹ and R ³³ are each independently a methyl group or an ethyl group. R ³² is preferably a phenylmethylene group or a phenylethylene group, more preferably R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethylene group.

  When the acrylic polymer dispersant has a tertiary amine as a basic group, from the viewpoint of dispersibility, the repeating unit represented by the following formula (ii) (hereinafter referred to as “repeating unit (ii)”) It is preferable to have.

In the formula (ii), R ³⁵ and R ³⁶ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. And may be an aralkyl group, and R ³⁵ and R ³⁶ may be bonded to each other to form a cyclic structure. ^R37 is a hydrogen atom or a methyl group. Z is a divalent linking group.

Further, for R ³⁵ and R ³⁶ in the formula (ii), as the alkyl group which may have a substituent, may be preferably used those exemplified as R ³¹ to R ³³ in the formula (i) it can.
Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ^{31 to} R ^{33 in} the above formula (i) should be preferably employed. Can do. In addition, as R ³⁵ and R ³⁶ in the above formula (ii) which may have a substituent, those exemplified as R ^{31 to} R ^{33 in} the above formula (i) may be preferably employed. it can.

Among these, R ³⁵ and R ³⁶ are preferably each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

Examples of the substituent that the alkyl group, aralkyl group or aryl group in R ^{31 to} R ³³ of the above formula (i) and R ³⁵ and R ³⁶ of the above formula (ii) may have include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group, etc. are mentioned.

In the above formulas (i) and (ii), examples of the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R ⁴³ — group, —COOR ⁴⁴ — group (wherein R ⁴³ and R ⁴⁴ are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), and the like are preferable. Is a —COO—R ⁴⁴ — group.
In the above formula (i), Y ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

  Although the content rate of the repeating unit represented by the said formula (i) is not specifically limited, From a dispersible viewpoint, it is represented by the content rate of the repeating unit represented by the said formula (i), and the said formula (ii). Preferably it is 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, based on the total content of repeating units. The amount is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.

  Further, the content of the repeating unit represented by the formula (i) in the total repeating units of the acrylic polymer dispersant is not particularly limited, but is preferably 1 mol% or more from the viewpoint of dispersibility, More preferably, it is 5 mol% or more, more preferably 10 mol% or more, more preferably 50 mol% or less, more preferably 30 mol% or less, and more preferably 20 mol% or less. More preferably, it is particularly preferably 15 mol% or less.

  Further, the content ratio of the repeating unit represented by the formula (ii) in all the repeating units of the acrylic polymer dispersant is not particularly limited, but is preferably 5 mol% or more from the viewpoint of dispersibility, More preferably, it is 10 mol% or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, more preferably 60 mol% or less, and 40 mol% or less. More preferably, it is more preferably 30 mol% or less, and particularly preferably 25 mol% or less.

  In addition, the acrylic polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter referred to as “repeating unit (hereinafter referred to as“ repeating unit ”) from the viewpoint of improving compatibility with binder components such as a solvent and improving dispersion stability. iii) ").).

In the above formula (iii), R ⁴⁰ is an ethylene group or a propylene group, R ⁴¹ is an alkyl group which may have a substituent, and R ⁴² is a hydrogen atom or a methyl group. n is an integer of 1-20.

The number of carbon atoms of the alkyl group which may have a substituent in R ⁴¹ of the above formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

  Further, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less from the viewpoints of compatibility with a binder component such as a solvent and dispersibility. More preferably, it is 5 or less.

  Further, the content ratio of the repeating unit represented by the formula (iii) in all the repeating units of the acrylic polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 2 mol% or more. More preferably, it is 4 mol% or more, more preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. When the amount is within the above range, compatibility with a binder component such as a solvent tends to be compatible with dispersion stability.

  In addition, the acrylic polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit”) from the viewpoint of improving the compatibility of the dispersing agent with a binder component such as a solvent and improving dispersion stability. (Iv) ").

In the above formula (iv), R ³⁸ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ³⁹ is a hydrogen atom or a methyl group.

The number of carbon atoms of the alkyl group which may have a substituent in R ³⁸ in the above formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, and more preferably 8 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ³⁸ in the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, a phenyl group, a methylphenyl group, and an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in R ³⁸ in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferred is 10 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group.
Examples of the substituent that the alkyl group may have in R ³⁸ include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. Further, the linear alkyl group represented by R ³⁸ includes both linear and branched chains.

  In addition, the content of the repeating unit represented by the formula (iv) in all the repeating units of the acrylic polymer dispersant is preferably 30 mol% or more, and 40 mol% or more from the viewpoint of dispersibility. More preferably, it is 50 mol% or more, more preferably 80 mol% or less, and even more preferably 70 mol% or less.

  The acrylic polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv). Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- Examples include (meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.

  The acrylic polymer dispersant does not have the A block having the repeating unit (i) and the repeating unit (ii), and the repeating unit (i) and the repeating unit (ii) from the viewpoint of further improving dispersibility. A block copolymer having a B block is preferable. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be remarkably improved. The B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).

  In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization and block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may be contained in two or more kinds in one A block. In that case, each repeating unit is randomly copolymerized in the A block. It may be contained in any form of block copolymerization.

  A repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block. Examples of such a repeating unit include the aforementioned (meth) acrylic acid ester-based unit. Examples include a repeating unit derived from a monomer. The content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.

  Repeating units other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonic acid Ether; repeating units derived from monomers such as N-methacryloylmorpholine. The content in the B block of the repeating units other than the repeating unit (iii) and the repeating unit (iv) is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.

  On the other hand, as a dispersant having both an acidic group and a basic group in the same molecule, for example, an unsaturated group-containing monomer having a basic group, an unsaturated group-containing monomer having an acidic group, and the like Acrylic polymer dispersants obtained by copolymerization of the unsaturated group-containing monomer and the like.

  Among these, the dispersant (f) is preferably a mixture of a dispersant having an acidic group and a dispersant having a basic group, from the viewpoint of ease of production. Examples thereof include a mixture with a molecular weight amine compound, and a compound of a phosphoric acid compound and an acrylic polymer dispersant having a basic group.

  Further, from the viewpoint of improving dispersion stability, (f) the dispersant is preferably used in combination with a pigment derivative described later.

<Other compounding components of colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention includes, in addition to the above-mentioned components, an adhesion improver such as a silane coupling agent, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment. Derivatives and the like can be appropriately blended.

(1) Adhesion improver The colored photosensitive resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphate group-containing adhesion improver, and the like are preferable.
As the type of silane coupling agent, various types such as epoxy, (meth) acrylic, amino and the like can be used alone or in combination of two or more.

Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Epoxyglycans such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, it is a silane coupling agent of epoxy silanes.
As the phosphate group-containing adhesion improver, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.

In the general formulas (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2, or 3.
These phosphoric acid group-containing adhesion improvers may be used alone or in combination of two or more.

(2) Surfactant The colored photosensitive resin composition of the present invention may contain a surfactant in order to improve coatability.

As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are unlikely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.
Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (DIC), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 (Nihon Unicar) ), FC4430 (manufactured by Sumitomo 3M), and the like.
In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

(3) Pigment derivative The colored photosensitive resin composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as phthalocyanine and quinophthalone are preferred.
Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group directly on the pigment skeleton or an alkyl group, an aryl group, a complex Examples thereof include those bonded via a ring group and the like, and preferably a sulfonic acid group. Further, a plurality of these substituents may be substituted on one pigment skeleton.

  Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.

(4) Photoacid generator A photoacid generator is a compound capable of generating an acid by ultraviolet rays, and has a crosslinking agent such as a melamine compound due to the action of an acid generated upon exposure. The crosslinking reaction will proceed. Among such photoacid generators, those having a high solubility in a solvent, particularly in a solvent used in a colored photosensitive resin composition, are preferable, for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl). ) Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, Diaryl iodonium such as p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoro Sulfonium organoboron complexes such as arsenate salt, aromatic sulfonate, tetrakis (pentafluorophenyl) borate salt, diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6- Triazine compounds such as bistrichloromethyltriazine and 2- (4-methoxyphenyl) -4,6-bistrichloromethyltriazine can be exemplified, but not limited thereto.

(5) Crosslinking agent To the colored photosensitive resin composition of the present invention, a crosslinking agent can be further added. For example, a melamine or guanamine compound can be used. Examples of these cross-linking agents include melamine or guanamine compounds represented by the following general formula (6).

In the formula (6), R ⁶¹ represents a —NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ is a —NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , one of R ⁶⁶ and R ^67, and R ⁶¹ represents R ^62, R ^63, one of R ⁶⁴ and R ⁶⁵ are -CH ₂ oR ⁶⁸ group in the case of an aryl group having from 6 to 12 carbon atoms, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ , independently of one another, represent hydrogen or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represent.
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and these phenyl group and naphthyl group include an alkyl group, an alkoxy group, a halogen atom, and the like. May be bonded to each other. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Alkyl group represented by R ⁶⁸ is, among the above, methyl group or an ethyl group, especially a methyl group.

  Melamine compounds corresponding to the general formula (6), that is, compounds of the following general formula (6-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.

In the formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH _2. Represents an OR ⁶⁸ group, and the remainder of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently of one another represents a hydrogen atom or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or Represents an alkyl group.

Further, guanamine compounds corresponding to the general formula (6), that is, compounds in which R ⁶¹ in the general formula (6) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.

Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.

  In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type. 0.1-15 mass% is preferable with respect to the total solid of a coloring photosensitive resin composition, and, as for the quantity at the time of using a crosslinking agent, Most preferably, it is 0.5-10 mass%.

(6) Mercapto compound It is also possible to add a mercapto compound as a polymerization accelerator and to improve the adhesion to the substrate.

  Mercapto compound types include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis. Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropioate , Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis 3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3 -Mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoiso) Butyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like mercapto compounds Or aliphatic polyfunctional mercapto compounds It is. These can be used alone or in combination of two or more.

<Ingredient compounding amount in colored photosensitive resin composition>
In the colored photosensitive resin composition of the present invention, the content ratio of (a) the colorant is usually 10% by mass or more and preferably 20% by mass or more with respect to the total solid content in the colored photosensitive resin composition. 25% by mass or more, more preferably 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and 35% by mass or less. Is more preferable. (A) By making the content rate of a coloring agent more than the said lower limit, there exists a tendency for sufficient optical density (OD) to be obtained, and sufficient image formability is obtained by making it below the said upper limit. It tends to be easy.

  In addition, when (a) the colorant contains an organic black pigment, the content ratio of the organic black pigment to (a) the colorant is not particularly limited, but is preferably 5% by mass or more, and more preferably 10% by mass or more. More preferably, it is more preferably 30% by mass or more, still more preferably 50% by mass or more, particularly preferably 70% by mass or more, most preferably 90% by mass or more, and usually 100% by mass. It is as follows. There exists a tendency which can improve light-shielding property by setting it as the said lower limit or more.

  Moreover, when (a) the coloring agent contains an organic coloring pigment, the content ratio of the organic coloring pigment to (a) the coloring agent is not particularly limited, but is preferably 5% by mass or more, and more preferably 10% by mass or more. More preferably, it is more preferably 30% by mass or more, still more preferably 50% by mass or more, particularly preferably 70% by mass or more, most preferably 90% by mass or more, Moreover, it is 100 mass% or less normally. There exists a tendency which can improve light-shielding property by setting it as the said lower limit or more.

  (B) The content rate of alkali-soluble resin is 5 mass% or more normally with respect to the total solid of the colored photosensitive resin composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more, Furthermore Preferably, it is 30% by mass or more, more preferably 35% by mass or more, particularly preferably 40% by mass or more, and usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably. It is 50 mass% or less. (B) By making the content rate of alkali-soluble resin more than the said lower limit, there exists a tendency which can suppress the fall of the solubility with respect to the developing solution of an unexposed part, and can suppress image development defect. Moreover, by setting it as the said upper limit or less, there exists a tendency which can suppress that the permeability | transmittance of the developing solution to an exposure part becomes high, and can suppress the sharpness of a pixel, or the fall of adhesiveness.

  (C) The content rate of a photoinitiator is 0.1 mass% or more normally with respect to the total solid of the colored photosensitive resin composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 1 It is at least mass%, more preferably at least 2 mass%, particularly preferably at least 3 mass%, and is usually at most 15 mass%, preferably at most 10 mass%, more preferably at most 6 mass%. (C) There exists a tendency which can suppress a sensitivity fall by making the content rate of a photoinitiator more than the said lower limit, and it suppresses the fall of the solubility with respect to the developing solution of an unexposed part by making it the said upper limit or less. There is a tendency that development defects can be suppressed.

(C) When using a polymerization accelerator together with a photopolymerization initiator, the content ratio of the polymerization accelerator is preferably 0.05% by mass or more based on the total solid content of the colored photosensitive resin composition of the present invention. Usually, it is 10 mass% or less, Preferably it is 5 mass% or less, A polymerization accelerator is 0.1-50 mass parts normally with respect to 100 mass parts of (c) photoinitiators, Especially 0.1-20 mass parts. It is preferable to use in the ratio. By setting the content ratio of the polymerization accelerator to the lower limit value or more, there is a tendency to suppress the decrease in sensitivity to the exposure light beam, and by setting the content ratio to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developer is suppressed. However, there is a tendency that development defects can be suppressed.
Further, the blending ratio of the sensitizing dye in the colored photosensitive resin composition of the present invention is usually 20% by mass or less, preferably 15% by mass or less in the total solid content in the colored photosensitive resin composition from the viewpoint of sensitivity. More preferably, it is 10 mass% or less.

  (D) The content of the photopolymerizable sum compound is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, based on the total solid content of the colored photosensitive resin composition of the present invention. It is. (D) By making the content rate of a photopolymerizable compound below the said upper limit, it becomes easy to suppress that the permeability of the developing solution to an exposed part becomes high, and to obtain a favorable image. . In addition, the lower limit of the content rate of (d) photopolymerizable compound is 1 mass% or more normally, Preferably it is 5 mass% or more, More preferably, it is 8 mass% or more.

  The colored photosensitive resin composition of the present invention has a solid content concentration of usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably (e) by using a solvent. It is prepared so that it may become 30 mass%.

  (F) The content of the dispersant is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less in the solid content of the colored photosensitive resin composition. 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable. Further, the content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less, 30 The amount is preferably at most 20 parts by mass, more preferably at most 20 parts by mass. (F) By making the content rate of a dispersing agent more than the said lower limit, there exists a tendency for sufficient dispersibility to be easy to be obtained, and the ratio of another component reduces relatively by making it below the said upper limit. There exists a tendency which can suppress that a sensitivity, platemaking property, etc. fall.

  When using an adhesion improving agent, the content ratio is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.00%, based on the total solid content in the colored photosensitive resin composition. 4 to 2% by mass. There is a tendency that the effect of improving the adhesion can be sufficiently obtained by setting the content ratio of the adhesion improver to the above lower limit value or more, and the sensitivity is lowered by setting it to the upper limit value or less, or a residue remains after development. There exists a tendency which can suppress becoming a defect.

  Moreover, when using surfactant, the content rate is 0.001-10 mass% normally with respect to the total solid in a colored photosensitive resin composition, Preferably it is 0.005-1 mass%, More preferably It is 0.01-0.5 mass%, Most preferably, it is 0.03-0.3 mass%. There is a tendency that the smoothness and uniformity of the coating film tends to be manifested by setting the content ratio of the surfactant to the lower limit value or more, and the smoothness and uniformity of the coating film is manifested by setting the content ratio to the upper limit value or less. It tends to be easy to suppress deterioration of other characteristics.

<Physical properties of colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention can be suitably used for forming a partition wall of an organic electroluminescent element, and exhibits a black color from the viewpoint of the characteristics of the organic electroluminescent element that is excellent in black reproducibility. The optical density (OD) per 1 μm thickness of the coating film is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, Usually 4.0 or less.

<Method for producing colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
Usually, (a) the colorant is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the colorant (a) is finely divided by the dispersion treatment, the resist coating characteristics are improved.

The dispersion treatment is usually preferably carried out in a system in which a part or all of (a) a colorant, (e) a solvent, (f) a dispersant, and (b) an alkali-soluble resin are used together (hereinafter referred to as dispersion). The mixture used for the treatment and the composition obtained by the treatment may be referred to as “ink”, “pigment dispersion” or “pigment dispersion for producing colored photosensitive resin composition”). In particular, it is preferable to use a polymer dispersant as the dispersant (f) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
Thus, in the step of producing a resist, it is preferable to produce a pigment dispersion for producing a colored photosensitive resin composition containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As (a) colorant, (e) organic solvent, and (f) dispersant that can be used in the pigment dispersion, those described as those that can be used in the colored photosensitive resin composition are preferably employed. be able to.

In addition, when a dispersion treatment is performed on a liquid containing all the components blended in the colored photosensitive resin composition, a highly reactive component may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When the (a) colorant is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.

[Cured product]
A cured product can be obtained by curing the colored photosensitive resin composition of the present invention. A cured product obtained by curing the colored photosensitive resin composition can be suitably used as a partition, particularly a colored partition, of an organic electroluminescence device having excellent light shielding properties.

[Partition wall]
Next, the partition using the colored photosensitive resin composition of this invention is demonstrated according to the manufacturing method.

(1) Support The support for forming the partition walls is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, but the material is, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone, or an epoxy resin. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.

The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, in order to improve surface properties such as adhesiveness. .
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Partition Wall The colored photosensitive resin composition of the present embodiment is used in the same manner as a known colored photosensitive resin composition for color filters, but the case of partition wall use will be described below. Usually, a colored photosensitive resin composition is supplied into a film or pattern by a method such as coating on a substrate on which a partition wall is to be provided, and the solvent is dried. Subsequently, exposure and development are performed. A pattern is formed by photolithography or the like. Then, a colored partition is formed on this board | substrate by performing additional exposure and a thermosetting process as needed.

(3) Formation of partition wall (3-1) Application of colored photosensitive resin composition The colored photosensitive resin composition of the present embodiment is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. Application of the colored photosensitive resin composition for the colored partition wall onto the transparent substrate can be performed by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and if it is too thin, it is difficult to increase the pigment concentration, and it is preferably in the range of 1 to 10 μm, more preferably in the range of 1 to 9 μm, and more preferably The range of 1 to 7 μm is preferable. In addition, it is important that the dry film thickness or the height of the partition wall finally formed is uniform over the entire area of the substrate. If the variation is large, an unevenness defect of the organic electroluminescent element is generated. Further, it may be supplied in a pattern by an inkjet method or a printing method.

(3-2) Drying of coating film The coating film after the colored photosensitive resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.
The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, (b) the alkali-soluble resin is decomposed, which may cause thermal polymerization and cause poor development. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on the coating film of the colored photosensitive resin composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. When exposure is performed using an exposure mask, the exposure mask is placed close to the coating film of the colored photosensitive resin composition, or the exposure mask is disposed at a position away from the coating film of the colored photosensitive resin composition, A method of projecting exposure light through the exposure mask may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength. The optical filter may be of a type that can control the light transmittance at an exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.
Exposure is usually normal, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 300 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 150 mJ / cm ² or less. In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less. It is.

(3-4) Development The partition wall according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image-exposing a coating film made of a colored photosensitive resin composition with the above light source. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.
The size, shape, and the like of the partition wall of the present invention formed as described above are appropriately adjusted according to the specifications of the organic electroluminescent element. However, the colored photosensitive resin composition of the present invention can eliminate the residue at the edge portion of the light emitting element when forming the colored partition walls of the organic electroluminescent element as described above. The height of the colored partition is usually about 1 to 7 μm.

[Organic electroluminescence device]
The organic electroluminescent element of the present invention comprises the cured product of the present invention as described above, for example, a partition wall.
For example, various organic electroluminescent elements are manufactured using a substrate including a partition wall manufactured by the method described above. The method for forming the organic electroluminescent element is not particularly limited, but preferably, after the pattern of the partition is formed on the substrate by the above method, the functional material is sublimated in a vacuum state, and the region within the region surrounded by the partition on the substrate is formed. An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method in which a film is vapor-deposited, a casting method, a spin coating method, or an ink jet printing method.

Examples of the type of organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition is formed on a glass substrate on which transparent electrodes are stacked, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in an opening surrounded by the partition. The On the other hand, in the top emission type, for example, a partition is formed on a glass substrate on which a metal electrode layer is stacked, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the partition. Created.
In addition, as a light emitting layer, the organic electroluminescent layer as described in Unexamined-Japanese-Patent No. 2009-146691 and patent 5734681 is mentioned. Further, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.

  The layer configuration is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may be a stacked configuration including two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and luminance.

  The organic electroluminescent element may be formed by separately separating RGB colors for each opening, or two or more colors may be stacked in one opening. Moreover, the organic electroluminescent element may be equipped with the sealing layer from a viewpoint of a reliability improvement. The sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescence device and reducing the luminous efficiency. Moreover, the organic electroluminescent element may be provided with the low reflection film in the interface with air from a viewpoint of the light extraction efficiency improvement. By disposing a low-reflection film at the interface between air and the element, it is possible to reduce the refractive index gap and suppress reflection at the interface. Examples of such a low reflection film include a moth-eye structure, a super multilayer film, and the like.

When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from the light emitting layer of a certain pixel from leaking to other pixels. Since it is necessary to prevent deterioration of image quality due to light reflection, it is preferable to provide light shielding properties to the partition walls constituting the organic electroluminescent element.
In addition, in the organic electroluminescence device, it is possible to provide electrodes on the upper surface and the lower surface of the partition wall.
Since it is necessary, the partition wall preferably has a high resistance and a low dielectric constant from the viewpoint of insulation. Therefore, when a colorant is used to impart light shielding properties to the partition walls, it is preferable to use an organic black pigment having a high resistance and a low dielectric constant.

[Image display device]
The image display device of the present invention includes the above-described organic electroluminescent element. As long as it includes an organic electroluminescent element, the type and structure of the image display device are not particularly limited, and for example, it can be assembled according to a conventional method using an active drive type organic electroluminescent element. For example, the image display device of the present invention is formed by a method as described in “Organic EL Display” (Ohm, published on August 20, 2004, by Shizushi Tokito, Chiba Adachi, and Hideyuki Murata). can do. For example, an organic electroluminescent element that emits white light and a color filter may be combined to display an image, or organic electroluminescent elements having different emission colors such as RGB may be combined to display an image.

[illumination]
The illumination of the present invention includes the above-described organic electroluminescent element. There is no restriction | limiting in particular about a model or a structure, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention. The organic electroluminescence element may be a simple matrix driving method or an active matrix driving method.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. In addition, organic electroluminescent elements having different emission colors may be combined so that each color is mixed to become white, or the color mixing ratio can be adjusted to provide a color adjustment function.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
The components of the colored photosensitive resin composition used in the following examples and comparative examples are as follows.

<Colorant-I>
Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (I-1))

<Colorant-II>
C. I. Pigment Blue 15: 6
<Colorant-III>
C. I. Pigment Violet 29
<Colorant-IV>
C. I. Pigment Orange 64

<Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 2,2′-azobis-2-methyl 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the alkali-soluble resin-I thus obtained was about 8400, and the acid value was 80 mgKOH / g.

<Alkali-soluble resin-II>

50 parts by mass of an epoxy compound (epoxy equivalent 264) having the above structure, 13.65 parts by mass of acrylic acid, 60.5 parts by mass of methoxybutyl acetate, 0.936 parts by mass of triphenylphosphine, and 0.032 parts by mass of paramethoxyphenol The mixture was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 90 ° C. with stirring until the acid value reached 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.38 parts by mass of trimethylolpropane (TMP), 4.90 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 0.8 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, the resin solution is diluted with methoxybutyl acetate and prepared to have a solid content of 50% by mass. The acid value is 110 mg KOH / g, and the polystyrene-soluble weight average molecular weight (Mw) of 7000 measured by GPC is alkali-soluble. Resin-II was obtained.

<Alkali-soluble resin-III>

50 parts by mass of an epoxy compound (epoxy equivalent 264) having the above structure, 13.65 parts by mass of acrylic acid, 60.5 parts by mass of methoxybutyl acetate, 0.936 parts by mass of triphenylphosphine, and 0.032 parts by mass of paramethoxyphenol The mixture was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 90 ° C. with stirring until the acid value reached 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.38 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with methoxybutyl acetate and prepared to have a solid content of 50% by mass. The acid value was 110 mgKOH / g, and the polystyrene-soluble weight average molecular weight (Mw) 2660 measured by GPC was alkali-soluble. Resin-III was obtained.

<Photopolymerization initiator-I>
A compound having the following chemical structure.

<Dispersant-I>
“DISPERBYK-LPN21116” manufactured by Big Chemie (an acrylic block copolymer comprising an A block having a quaternary ammonium base and a tertiary amino group in the side chain and a B block having no quaternary ammonium base and an amino group. (Amine value is 70 mgKOH / g. It has no acidic group.)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a).

<Dispersant-II>
Big Chemie “DISPERBYK-111” (polyether copolymer having a phosphate group as an adsorptive group at its terminal. Acid value is 129 mgKOH / g.)

<Dispersant-III>
Big Chemie "DISPERBYK-167" (urethane-based polymer dispersant. Amine value is 23 mgKOH / g. It has no acidic group.)

<Dispersant-IV>
Big Chemie "DISPERBYK-2000" (acrylic copolymer. Amine value is 10 mgKOH / g. It has no acidic group.)

<Dispersant-V>
Big Chemie's “DISPERBYK-180” (a dispersant having a salt structure obtained by neutralizing an acrylic copolymer having a phosphate group as an adsorbing group with an amine neutralization. The amine value is 116 mgKOH / g. The acid value is 116 mgKOH / g. )

<Dispersant-VI>
Evonik “TEGO DISPERS 685” (modified polyester of comb branch polymer. Amine value is 40 mg KOH / g. Acid value is 50 mg KOH / g.)

<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxy-1-butanol

<Photopolymerizable compound-I>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate

<Surfactant>
DIC Corporation Mega Fuck F-559
<Additives>
Nippon Kayaku Co., Ltd., KAYAMER PM-21 (phosphate containing methacryloyl group)

<Preparation of pigment dispersions 1-3>
The colorant, the alkali-soluble resin, the solvent, and the dispersant were mixed so as to have the blending ratio shown in Table 1. This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and dispersion were separated by a filter to prepare pigment dispersions 1 to 3.

[Examples 1 and 2 and Comparative Example 1]
Using the pigment dispersions 1 to 3 prepared above, each component was added so that the ratio in the solid content was the mixing ratio in Table 2, and the total solid content was 22% by mass, and the solvent content ratio (mass) A solvent was added so that the ratio) was solvent-I: solvent-II = 80: 20, and the mixture was stirred and dissolved to prepare a colored photosensitive resin composition.

<Method for making partition wall substrate>
Each colored photosensitive resin composition was applied onto an ITO substrate (a glass substrate having an ITO deposition thickness of 700 mm) using a spinner. Subsequently, it heated and dried on the hotplate at 100 degreeC for 80 second, and the coating film was formed.
The obtained coating film was subjected to an exposure treatment using an exposure mask in which line-shaped covering portions having a width of 260 μm were arranged every 60 μm. The exposure gap (distance between the exposure mask and the coated surface) was 5 μm. The irradiation light intensity at a wavelength 365nm is used ultraviolet is 32 mW / cm ^2, the exposure amount was 60 mJ / cm ^2. Moreover, ultraviolet irradiation was performed under air.

Subsequently, using a developer composed of a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide), shower development was performed at 25 ° C. with a water pressure of 0.05 MPa, and then development was stopped with pure water, followed by washing with water. Washed with spray. The shower development time was adjusted between 10 and 120 seconds, and was 1.2 times as long as the unexposed coating film was dissolved and removed.
By these operations, a pattern from which unnecessary portions were removed was obtained. The substrate on which the pattern was formed was heated in an oven at 230 ° C. for 30 minutes to cure the pattern, thereby obtaining a pattern having a thickness of 2.0 μm, thereby preparing a partition wall substrate.

<Formation of organic electroluminescence device>
On the entire surface of the manufactured partition wall substrate, molybdenum oxide as a hole injection layer has a thickness of 10 nm, and 4,4′-bis [N- (9-phenanthryl) -N-phenyl-amino] biphenyl (PPD) as a hole transport layer. The film thickness is 60 nm, the light-emitting layer is tris (8-hydroxyquinolinato) aluminum (Alq3) film thickness is 60 nm, the electron injection layer is lithium fluoride film thickness is 0.5 nm, and the cathode is aluminum film thickness is 80 nm. The organic electroluminescence device was fabricated by sequentially stacking the layers on the substrate by vacuum deposition.
Next, a desiccant was affixed to the concave portion of the sealing glass having a concave portion at the center, and a UV curable resin was applied to the frame portion around the concave portion. The concave portion of the sealing glass is arranged so as to cover all of the organic electroluminescent elements and the line pattern on the partition substrate, the sealing glass is attached to the partition substrate, UV is applied to the UV curable resin and cured, and a hollow structure is formed. The device for organic electroluminescent element evaluation was produced by sealing.

<Observation of organic electroluminescence device>
A direct current of 300 μA was passed between the electrodes of the produced organic electroluminescence device to cause the organic electroluminescence device to emit light. The center part of the organic electroluminescent element was observed with an optical microscope at a magnification of 10 times. The photograph taken is shown in FIGS. The presence or absence of a non-light emitting area was determined from the captured photograph. The results are shown in Table 2.

<Evaluation of optical density>
Each colored photosensitive resin composition was applied onto a glass substrate using a spinner. Subsequently, it heated and dried on the hotplate at 100 degreeC for 80 second, and the coating film was formed.
The obtained coating film was exposed. The irradiation light intensity at a wavelength 365nm is used ultraviolet is 32 mW / cm ^2, the exposure amount was 60 mJ / cm ^2. Moreover, ultraviolet irradiation was performed under air. Next, the substrate was heated in an oven at 230 ° C. for 30 minutes to cure the coating film to obtain a cured film having a thickness of 3 μm. The optical density of the cured film was measured using a transmission densitometer D200-II manufactured by Gretag Macbeth. The optical density per unit thickness (unit OD) was calculated by dividing the optical density by the thickness of the cured film. The results are shown in Table 2.

  In the organic electroluminescent element using the colored photosensitive resin composition of Comparative Example 1, a non-light emitting region was observed in the vicinity of the partition wall of the light emitting portion. On the other hand, in the organic electroluminescent element using the colored photosensitive resin composition of Examples 1 and 2, no non-light emitting region was observed.

  Since the dispersant used in Examples 1 and 2 contains both a basic group and an acidic group, the electrostatic interaction acting between the basic group and the acidic group and the van der Waals force acting between the parent solvent groups. To form a polymer complex. It is considered that the polymer complex is dissolved or dispersed in the developer by the coordination of the basic ion of the developer to the acidic group on the surface of the polymer complex. Therefore, in the colored photosensitive resin compositions of Examples 1 and 2, it is considered that the dispersant on the substrate surface was completely removed in the development process, and no non-light emitting region was generated in the light emitting portion of the organic electroluminescent element.

  On the other hand, in the colored photosensitive resin composition of Comparative Example 1, since the dispersant does not contain an acidic group, the dispersant remains on the substrate surface in the development process, and acts as a carrier movement resistance or quencher in the organic electroluminescence device. Therefore, it is considered that a non-light emitting region has occurred.

  As described above, as in Examples 1 and 2, by using a dispersant containing an acidic group and a basic group, generation of a non-light emitting region of an organic electroluminescent element can be eliminated while maintaining high light shielding performance. Can do.

<Reference example>
[Reference Examples 1 to 7]
For the purpose of verifying the occurrence or non-occurrence of the non-emission region of the organic electroluminescence device, each component was added so that the ratio in the solid content was the mixing ratio shown in Table 3, and the total solid content was 22% by mass. A solvent was added so that the content ratio (mass ratio) would be solvent-I: solvent-II = 80: 20, and the mixture was stirred and dissolved to prepare a photosensitive resin composition.

Using the obtained photosensitive resin composition, a partition wall substrate was produced by the method described above. However, in Reference Example 6, a 0.20% by mass TMAH aqueous solution was used as the developer, and in Reference Example 7, a 0.04% by mass KOH (potassium hydroxide) aqueous solution was used.
Using the obtained partition wall substrate, an organic electroluminescence device was produced by the above-described method, and the occurrence of a non-light emitting region near the partition wall of the light emitting portion was determined by the above-described method. The results are shown in Table 3.

Comparing the results of Comparative Example 1 and Reference Examples 1 and 2, both Comparative Example 1 and Reference Example 1 containing Dispersant I have a non-light-emitting region, whereas Reference Example 2 containing no dispersant at all. There is no non-light emitting area. From this, it can be concluded that the non-light emitting region of the light emitting part of the organic electroluminescent element is caused by the dispersant.
From the results of Reference Examples 1 and 3 to 7, when a dispersant containing no acidic group was used as in Reference Examples 1, 3 and 4, a non-light emitting region was present, while on the other hand, as in Reference Examples 5 to 7 It can be seen that the use of a dispersant containing an acidic group and a basic group can suppress the occurrence of a non-light emitting region. Furthermore, from the results of Reference Examples 5 and 6, it was found that this effect can be expected even when a 0.20% by mass TMAH aqueous solution or a 0.04% by mass KOH aqueous solution is used as the developer.

Claims (13)

A partition of an organic electroluminescent device comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound, (e) a solvent, and (f) a dispersant. A colored photosensitive resin composition for forming,
The colored photosensitive resin composition, wherein the dispersant (f) contains an acidic group and a basic group.   The colored photosensitive resin composition according to claim 1, wherein the (a) colorant contains an organic black pigment. The coloring according to claim 2, wherein the organic black pigment contains a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound. Photosensitive resin composition.
(In formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N = CH ₂ , N = CHR ¹¹ , N = CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
And at least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or carbon. It is an alkynyl group of formula 2-12. )   The colored photosensitive resin composition according to any one of claims 1 to 3, wherein (a) the colorant contains at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment, and a purple pigment. object.   The coloring according to claim 4, wherein the colorant (a) contains at least one selected from the group consisting of a red pigment and an orange pigment and at least one selected from the group consisting of a blue pigment and a purple pigment. Photosensitive resin composition.   The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the basic group contained in the dispersant (f) is a tertiary amino group or a quaternary ammonium base.   The colored photosensitive resin composition according to claim 1, wherein the acidic group contained in the dispersant (f) is a phosphoric acid group.   The colored photosensitive resin composition of any one of Claims 1-7 whose optical density per 1 micrometer of film thickness of the hardened coating film is 1.0 or more.   Hardened | cured material comprised with the colored photosensitive resin composition of any one of Claims 1-8.   An organic electroluminescent element provided with the hardened | cured material of Claim 9.   The image display apparatus containing the organic electroluminescent element of Claim 10.   The illumination containing the organic electroluminescent element of Claim 10. A pigment dispersion for producing a colored photosensitive resin composition for forming a partition wall of an organic electroluminescent device comprising (a) a colorant, (e) a solvent, and (f) a dispersant,
The pigment dispersion liquid, wherein the dispersant (f) contains an acidic group and a basic group.