JP2019015966A - Photosensitive coloring composition, cured product, colored spacer, and image display device - Google Patents

Abstract

To provide a photosensitive coloring composition capable of forming a colored spacer which suppresses light leakage at a wavelength of 400-500 nm, is excellent in light-shielding properties, and is excellent in mechanical characteristics, and to provide a colored spacer and an image display device including such a colored spacer.SOLUTION: The photosensitive coloring composition of the present invention contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound. The content ratio of the colorant (a) is 23 mass% or less in the total solid content of the photosensitive coloring composition. The colorant (a) contains a yellow pigment, and a red pigment and/or an orange pigment. The content ratio of the yellow pigment in the colorant (a) is 40 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive coloring composition and the like. Specifically, for example, a photosensitive coloring composition preferably used for forming a colored spacer or the like in a color filter such as a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, a colored spacer, and an image including the colored spacer. The present invention relates to a display device.

A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage to the liquid crystal. On the other hand, many of the members constituting the cell of the liquid crystal display are formed by a method using a photosensitive composition typified by photolithography. This photosensitive composition is expected to be widely applied in the future because it is easy to form a fine structure and is easy to process a large area substrate.
Also, backlights used in liquid crystal displays are widely used in the mobile terminal and television industries because of their high resolution, low cost, and thin form factor.

  Recently, in order to cope with higher definition and higher brightness of color liquid crystal displays, in active matrix liquid crystal displays, color filter on-array method (COA method) in which color filters are provided on the TFT element substrate side, A black matrix on array method (BOA method) in which only the black matrix is provided on the TFT element substrate side has been proposed. According to this method, compared with the case where a black matrix is formed on the color filter side, it is not necessary to take an alignment margin with the active element side, so that the aperture ratio can be increased, and as a result, higher luminance can be achieved. Can be planned. Such a black matrix structure is required to have high light shielding properties and to suppress light leakage in the visible light region as much as possible.

Also, with the simplification of the structure of the liquid crystal display and the manufacturing process, so-called column spacers, colored spacers that integrate a photo spacer and a black matrix are used to keep the distance between two substrates in a liquid crystal display constant. Has also been developed. As such a colored spacer, a colored spacer using a plurality of types of organic colored pigments as a pigment has been proposed (see, for example, Patent Documents 1 and 2).
On the other hand, as disclosed in Patent Documents 3 to 5, there is also proposed a liquid crystal display in which one or two or more color filter layers are provided on the facing portion of the colored spacer in the frame portion.

JP 2012-181509 A International Publication No. 2013/062011 Korean Published Patent No. 10-2013-0015734 Korean Published Patent No. 10-2014-0119912 Korean Published Patent No. 10-2017-0017447

As a result of studies by the present inventors, among various panel structures, particularly in a liquid crystal display equipped with an LED backlight, in the case of a structure in which a blue color filter layer is provided on the facing portion of the colored spacer in the frame portion. Is easy to transmit the blue light component derived from the LED, and the colored spacer formed using the photosensitive coloring composition described in Patent Documents 1 and 2 suppresses light leakage at a wavelength of 400 to 500 nm and has a light shielding property. It was found difficult to achieve both.
In addition, when manufacturing a liquid crystal display, since a process of crimping a substrate having a colored spacer and a counter substrate is performed, the colored spacer is original when external pressure is removed even if it is deformed by external pressure in the crimping process. Therefore, characteristics that return to the shape of the material, that is, mechanical characteristics such as elastic recovery rate, are required.

  The present invention has been made in view of the above circumstances, and provides a photosensitive coloring composition capable of forming a colored spacer excellent in light shielding properties and mechanical properties, with light leakage at a wavelength of 400 to 500 nm being suppressed. For the purpose.

As a result of intensive studies by the present inventors to solve the above problems, a specific pigment is used as a colorant, the content ratio of the pigment is set to a specific range, and the content ratio of the colorant is set to a specific range. Thus, the present inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention has the following configurations [1] to [8].

[1] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound,
The content ratio of the colorant (a) is 23% by mass or less in the total solid content of the photosensitive coloring composition,
(A) the colorant comprises a yellow pigment, a red pigment and / or an orange pigment;
(A) The photosensitive coloring composition characterized by the content rate of the said yellow pigment in a coloring agent being 40 mass% or more.
[2] The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, and C.I. I. The photosensitive coloring composition according to [1], comprising at least one selected from the group consisting of CI Pigment Yellow 150.
[3] The red pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 254, and C.I. I. The photosensitive coloring composition as described in [1] or [2] containing at least 1 sort (s) chosen from the group which consists of pigment red 272.
[4] The orange pigment is C.I. I. Pigment orange 13, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. The photosensitive coloring composition in any one of [1]-[3] containing at least 1 sort (s) chosen from the group which consists of pigment orange 72.

[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the content of the colorant (a) is 1% by mass or more in the total solid content of the photosensitive coloring composition. .
[6] The photosensitive coloring composition according to any one of [1] to [5], which is for forming a colored spacer.

[7] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [6].
[8] A colored spacer composed of the cured product according to [7].
[9] An image display device comprising the colored spacer according to [8].

  According to the present invention, light leakage at a wavelength of 400 to 500 nm is suppressed, a light-sensitive coloring composition, a cured product, a colored spacer, and the like that can form a colored spacer having excellent light shielding properties and excellent mechanical properties. An image display device including a colored spacer can be provided.

FIG. 1 is an emission spectrum of a light source used for color tone evaluation.

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 photosensitive coloring composition or the ink described later.
In the present invention, “weight average molecular weight” refers to polystyrene-reduced 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, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

In the present specification, the percentage and part expressed by “mass” are synonymous with the percentage and part expressed by “weight”.
In the present specification, specific examples of the pigment may be indicated by a pigment number, but terms such as “CI Pigment Red 2” mean a color index (CI).

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Contains an ethylenically unsaturated compound as an essential component, and if necessary, an adhesion improver such as a silane coupling agent, an interface It contains other compounding components such as activators (coating improvers), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, development improvers, UV absorbers, antioxidants, etc. The component is used in a state dissolved or dispersed in a solvent.

  The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound. The content ratio of the (a) colorant is 23% by mass or less in the total solid content of the photosensitive coloring composition, and the (a) colorant includes a yellow pigment, a red pigment and / or an orange pigment. And (a) a content ratio of the yellow pigment in the colorant is 40% by mass or more.

<(A) Colorant>
The (a) colorant contained in the photosensitive coloring composition of the present invention is a component that colors the photosensitive coloring composition. (A) By containing a colorant, desired light absorption characteristics can be obtained. (A) As the colorant, a pigment or a dye may be used.

In the photosensitive coloring composition of the present invention, (a) the colorant contains a yellow pigment, a red pigment and / or an orange pigment, and (a) the content ratio of the yellow pigment in the colorant is 40% by mass. That's it.
Since the yellow pigment has a maximum absorption peak wavelength in the vicinity of a wavelength of 400 to 450 nm in the absorption spectrum, light leakage at a wavelength of 400 to 500 nm can be efficiently reduced by including the yellow pigment. It is considered that the light leakage can be reduced to a practically sufficient level by setting the ratio to the lower limit value or more. On the other hand, since there is little absorption below wavelength 400nm, there is little overlap with the absorption band of a photoinitiator, and it is effective also from a viewpoint of photocurability and sensitivity.
In addition, since the red pigment and the orange pigment have a maximum absorption peak wavelength in the vicinity of a wavelength of 450 to 600 nm in the absorption spectrum, it is considered that the optical density (OD) is increased by further containing the red pigment and / or the orange pigment. . Since the maximum wavelength of the absorption peak of the red pigment is longer than that of the orange pigment, it is preferable to include a red pigment from the viewpoint of optical density (OD). On the other hand, light leakage suppression at a wavelength of 400 to 500 nm is preferable. From the viewpoint, an orange pigment is preferably included.

  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. Among these, from the viewpoint of dispersibility and reliability, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable. I. Pigment Yellow 138, 139, and 150 are more preferable, and C.I. I. Pigment Yellow 139 is particularly preferable.

  (A) The content of the yellow pigment in the colorant is not particularly limited as long as it is 40% by mass or more, but is preferably 50% by mass or more, and preferably 60% by mass or more from the viewpoint of suppressing the transmittance at a wavelength of 400 to 500 nm. Is more preferably 70% by mass or more, and particularly preferably 75% by mass or more. On the other hand, from the viewpoint of optical density (OD), 90% by mass or less is preferable, and 80% by mass or less is more preferable.

  On the other hand, as a red pigment, 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. Among these, from the viewpoint of light shielding properties and dispersibility, C.I. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254. In terms of dispersibility and light shielding properties, C.I. I. Pigment Red 177, 254, and 272 are preferably used. When the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. I. More preferably, CI pigment red 254 and 272 are used.

  Examples of the orange pigment (orange pigment) 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 13, 43, 64, 72 are preferably used. When the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. C. I. More preferably, CI pigment oranges 64 and 72 are used. I. Pigment Orange 64 is particularly preferable.

  (A) The total content of the red pigment and the orange pigment in the colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and 15% by mass or more. Is more preferably 20% by mass or more, usually 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and more preferably 30% by mass or less. Particularly preferred. When it is at least the lower limit, the optical density (OD) tends to be high, and when it is at most the upper limit, the transmittance at a wavelength of 400 to 500 nm tends to be sufficiently suppressed.

  When (a) the colorant contains a red pigment, the content ratio of the red pigment in (a) the colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more. More preferably, 15% by mass or more is particularly preferable, 20% by mass or more is most preferable, and usually 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and further more preferably 35% by mass or less. 30% by mass or less is particularly preferable. When it is at least the lower limit, the optical density (OD) tends to be high, and when it is at most the upper limit, the transmittance at a wavelength of 400 to 500 nm tends to be sufficiently suppressed.

  When the colorant contains an orange pigment, the content ratio of the orange pigment in the colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more. More preferably, 15% by mass or more is particularly preferable, 20% by mass or more is most preferable, and usually 60% by mass or less, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 35% by mass or less is more preferable. 30 mass% or less is especially preferable. There is a tendency that it is easy to achieve both optical density (OD) and transmittance suppression at a wavelength of 400 to 500 nm by setting it to the lower limit value or more, and the transmittance at a wavelength of 400 to 500 nm is sufficiently set by setting the upper limit value or less. There is a tendency to be able to suppress.

  (A) The colorant may contain a colorant other than a yellow pigment, a red pigment, and an orange pigment (hereinafter abbreviated as “other colorant”). Examples of other colorants include pigments and dyes. Pigments are preferable from the viewpoint of heat resistance, and organic pigments are preferable from the viewpoint of color tone, photocurability, and sensitivity.

  Examples of the pigment include organic coloring pigments such as a blue pigment, a purple pigment, a green pigment, and a brown pigment.

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. Among these, from the viewpoint of light shielding properties, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, and more preferably C.I. I. Pigment Blue 15: 6,16.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used. When the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. C. I. More preferably, CI Pigment Blue 60 is used. On the other hand, as described in Korean Registered Patent No. 10-1840984, C.I. I. It is preferable to use CI Pigment Blue 16.

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. Among these, from the viewpoint of light shielding properties, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.
On the other hand, from the viewpoint of dispersibility, C.I. I. Pigment violet 29 is preferably used.

  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, 58, 59. . Among these, from the viewpoint of dispersibility, C.I. I. And CI Pigment Green 7 and 36.

  Examples of the brown pigment (brown pigment) include C.I. I. CI pigment brown 23, 25, 26, 28, 38, 41, 83, 93. Among these, from the viewpoint of achieving both near-infrared transparency and light-shielding properties, C.I. I. Pigment brown 26, 28, 83, 93.

  Among these organic coloring pigments, from the viewpoint of color tone, it is preferable that the content ratio of, for example, a blue pigment and a purple pigment is low. From such a viewpoint, the total content ratio of the blue pigment and the violet pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and further 20% by mass or less. Is particularly preferable, and 0% by mass is most preferable. That is, it is most preferable that (a) the colorant does not contain a blue pigment and a violet pigment.

  (A) The content ratio of the blue pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass. preferable. By setting it to the upper limit value or less, there is a tendency that a good color tone is obtained.

  (A) The content ratio of the purple pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass. preferable. By setting it to the upper limit value or less, there is a tendency that a good color tone is obtained.

  On the other hand, from the viewpoint of light shielding properties, a blue pigment and / or a violet pigment may be included. In that case, the total content of the blue pigment and the violet pigment in (a) the colorant is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and 10% by mass. The above is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, 20% by mass or less is further more preferable, and 15% by mass or less is particularly preferable. Optical density (OD) tends to increase by setting it to the lower limit or higher, and transmittance at a wavelength of 400 to 500 nm tends to decrease by setting the upper limit or lower.

  Moreover, a black pigment may be included as another colorant. Examples of black pigments include organic black pigments and inorganic black pigments. Examples of organic black pigments include organic compounds containing at least one selected from the group consisting of a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound A black pigment is mentioned.

In formula (1), 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 be bonded directly to each other, or can be bonded 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 (1) has the following core structure (however, substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable. is there.

  When the compound represented by general formula (1) 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 (1) is anionic, it is preferably a similar salt.

In the substituents of the general formula (1) and their definitions, the following is preferable because the shielding rate tends to increase. 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 preferably each independently 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 , and 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 is preferably a compound represented by the following general formula (2) and / or a geometric isomer of the compound, and more preferably a compound represented by the following general formula (2).

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. Further, at the time of dispersion, the sulfonic acid derivative of the compound represented by the general formula (1) or the sulfonic acid derivative of the compound, particularly the sulfonic acid derivative of the compound represented by the general formula (2) or the geometry of the compound When an isomer of a sulfonic acid derivative is present, dispersibility and storage stability may be improved.
In addition, as an organic black pigment, from the viewpoint of optical properties and reliability, an organic black pigment described in Korean Published Patent No. 10-2018-0052502, or described in Korean Published Patent No. 10-2018-0052864 is disclosed. It is preferable to use organic black pigments.

  Other organic black pigments include aniline black, cyanine black, perylene black and the like. Carbon black which is an inorganic black pigment may be used. Examples of carbon black include the following carbon black.

Made by 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 V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color1 or Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark, the same applies hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, RE, 99, REG 99 (registered trademark, RE 4) REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8
Made by Birler: RAVEN (registered trademark, the same applies hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN10RA, RAVEN10RA, RAVEN890H, RAVEN890H, RAVEN890H, RAVEN890H , 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.

These pigments are preferably used in a dispersed state 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 photosensitive coloring composition, 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 is measured by fully diluted photosensitive coloring composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, According to concentration) and measured at 25 ° C.

In addition to the pigments described above, dyes may be used as other colorants. Examples of dyes that can be used as other colorants 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 contains a carboxyl group or a hydroxyl group. For example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, or a carboxyl group-containing resin is used. Urethane resins, novolac resins, polyvinylphenol resins, and the like can be mentioned. Among them, (b1) epoxy (meth) acrylate resins (b2) acrylic resins are preferably used from the viewpoint of excellent plate making properties. These can be used individually by 1 type or in mixture of multiple types.

<(B1) Epoxy (meth) acrylate resin>
(B1) The epoxy (meth) acrylate resin is a reaction product of an epoxy resin (epoxy compound) and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. The resin obtained by further reacting the hydroxyl group produced by the reaction with a polybasic acid and / or its anhydride.
In addition, before reacting the polybasic acid and / or anhydride thereof with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and / or anhydride thereof is reacted. Resins obtained by reaction are also included in the (b1) epoxy (meth) acrylate resin.

Moreover, the resin obtained by making the carboxyl group of resin obtained by the said reaction react with the compound which has a functional group which can react further is also contained in the said (b1) epoxy (meth) acrylate type resin.
As described above, the epoxy (meth) acrylate resin does not substantially have an epoxy group in terms of chemical structure and is not limited to “(meth) acrylate”, but an epoxy compound (epoxy resin) is a raw material. In addition, since “(meth) acrylate” is a representative example, it is named in accordance with conventional usage.

  Specifically, the (b1) epoxy (meth) acrylate resin used in the present invention is the following epoxy (meth) acrylate resin (b1-1) and / or epoxy (meth) acrylate resin (b1-2). (Hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth) acrylate resin”) is preferably used from the viewpoint of developability and reliability.

<Epoxy (meth) acrylate resin (b1-1)>
It is obtained by adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Obtained alkali-soluble resin.
<Epoxy (meth) acrylate resin alkali-soluble resin (b1-2)>
An α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and a polyhydric alcohol and a polybasic acid and / or anhydride thereof are added. An alkali-soluble resin obtained by reacting.

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 two or more phenolic hydroxyl groups, and may be a monomer or a polymer.
The types of epoxy resins used as raw materials are cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type epoxy resins, biphenyl novolac type epoxy resins, naphthalene novolak type An epoxy resin, an epoxy resin that is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and an epihalohydrin, an adamantyl group-containing epoxy resin, a fluorene type epoxy resin, and the like can be suitably used. Those having an aromatic ring in the main chain can be suitably used.

  Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin (for example, “jER (registered trademark, the same applies hereinafter) -828”, “jER-1001”, “jER-1002” manufactured by Mitsubishi Chemical Corporation). , “JER-1004”, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, “jER-807” manufactured by Mitsubishi Chemical Corporation, “ jER-4004P ”,“ jER-4005P ”,“ jER-4007P ”,“ NER-7406 ”(epoxy equivalent 350, softening point 66 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenyl glycidyl ether (For example, “jER-YX4000” manufactured by Mitsubishi Chemical Corporation), a phenol novolac type epoxy resin (for example, “EPPN (registered trademark, the same shall apply hereinafter) -201” manufactured by Honka Pharmaceutical Co., Ltd., “jER-152”, “jER-154” manufactured by Mitsubishi Chemical Corporation, “DEN-438” manufactured by Dow Chemical Co., Ltd.) o, m, p-) cresol novolac type epoxy resin (for example, “EOCN (registered trademark, the same applies hereinafter) -102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl Isocyanurate (for example, “TEPIC (registered trademark)” manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resin (for example, “EPPN-501”, “EPPN-502”, “EPPN-503” manufactured by Nippon Kayaku Co., Ltd.) ), Alicyclic epoxy resins (“Celoxide (registered trademark, the same shall apply hereinafter) 2021P”, “Celoxide EHPE” manufactured by Daicel Corporation), dicyclope Epoxy resin obtained by glycidylation of phenol resin by reaction of tadiene and phenol (for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), the following general formulas (B1) to (B4) The epoxy resin etc. which are represented by these can be used suitably. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1), and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2) NC-3000 ”,“ ESF-300 ”manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like can be given as an epoxy resin represented by the following general formula (B4).

In the said general formula (B1), a is an average value and represents the number of 0-10. R ¹¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. A plurality of R ¹¹¹ present in one molecule may be the same or different from each other.

In the said general formula (B2), b is an average value and represents the number of 0-10. R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. A plurality of R ¹²¹ present in one molecule may be the same or different from each other.

  In the general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, one or more adamantane structures are included in the molecular structure. c represents 2 or 3.

In the general formulas (B3-1) and (B3-2), R ^{131 to} R ¹³⁴ and R ^{135 to} R ¹³⁷ each independently represent an adamantyl group, a hydrogen atom, or a substituent which may have a substituent. An alkyl group having 1 to 12 carbon atoms that may have or a phenyl group that may have a substituent. * Represents a bond.

In the general formula (B4), p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ¹⁴³ and R ¹⁴⁴ each independently represents an alkylene group having 1 to 4 carbon atoms. x and y each independently represents an integer of 0 or more.

  Among these, it is preferable to use an epoxy resin represented by any one of the general formulas (B1) to (B4).

As α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2 -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2 -(Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- ( (Meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) Acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ- Monomers to which lactones such as butyrolactone and δ-valerolactone are added, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and (anhydrous) Acids such as acid, (anhydrous) phthalic acid, (anhydrous) maleic acid ( Anhydride) was added to the monomer, and (meth) acrylic acid dimer.
Among these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

  As a method of adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin, a known method can be used. For example, an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is reacted with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. be able to. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .

The epoxy resin, the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may all be used alone. Two or more kinds may be used in combination.
The amount of α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. Is more preferable, and the range of 0.7 to 1.1 equivalents is more preferable. By making the amount of α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group more than the above lower limit, deficiency in the amount of unsaturated groups introduced can be suppressed, Subsequent reaction with the polybasic acid and / or its anhydride tends to be sufficient. On the other hand, by setting it to the upper limit or less, it is possible to suppress the remaining unreacted α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and to improve the curing characteristics. There is a tendency to be easy.

  Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

  Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

  A known method can also be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid having a carboxyl group to epoxy resin. The desired product can be obtained by continuing the reaction under the same conditions as in the addition reaction of the carboxylic acid ester. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, The degree is preferably in the range of 20 to 140 mgKOH / g. There exists a tendency for alkali developability to become favorable by setting it as the said lower limit or more, and there exists a tendency for hardening performance to become favorable by setting it as the said upper limit or less.

  In addition, a polybranched structure may be introduced by adding a polyhydric alcohol such as trimethylolpropane, pentaerythritol, and dipentaerythritol during the addition reaction of the polybasic acid and / or anhydride thereof.

  The carboxyl group-containing epoxy (meth) acrylate resin is generally used as a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. After mixing the basic acid and / or its anhydride, or in the reaction product of the epoxy resin and α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, It is obtained by heating after mixing a polybasic acid and / or its anhydride and a polyhydric alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited. Either present in a mixture of a reaction product of an epoxy resin with an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group and a polyhydric alcohol by heating. A polybasic acid and / or an anhydride thereof undergo an addition reaction with respect to the hydroxyl group.

  As the carboxyl group-containing epoxy (meth) acrylate resin, in addition to the above-mentioned ones, Korean Published Patent No. 10-2013-0022955, Korean Registered Patent No. 10-0965189, Japanese Patent Laid-Open No. 2005-165294, Examples described in Japanese Unexamined Patent Publication No. 2006-312704.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more. More preferably, it is 2,500 or more, usually 10,000 or less, preferably 8,000 or less, more preferably 6,000 or less, still more preferably 5,000 or less, particularly preferably 4,000 or less. When the amount is not less than the lower limit value, the solubility in the developer tends to be suppressed, and when the amount is not more than the upper limit value, the solubility in the developer tends to be favorable.

  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, preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and 100 mgKOH / g. g or less is more preferable, and 50 mgKOH / g or less is particularly preferable. When the amount is not less than the lower limit, moderate development solubility tends to be obtained, and when the amount is not more than the upper limit, there is a tendency that development is progressed excessively and film dissolution can be suppressed.

  The chemical structure of the epoxy (meth) acrylate resin (b1) is not particularly limited. For example, the epoxy (meth) acrylate resin (b1-A) having a partial structure (1) represented by the following general formula (I) (Hereinafter, it may be abbreviated as “epoxy (meth) acrylate resin (b1-A)”). Since the epoxy (meth) acrylate resin (b1-A) has three or more (meth) acryloyloxy groups in the partial structure represented by the formula (I), the amount of ethylenic double bonds in one molecule of the resin is In many cases, when a colored spacer is formed using a photosensitive coloring composition containing the resin, the crosslinking density is increased, elution of impurities into the solvent is suppressed and high reliability can be ensured, and the spacer has a high crosslinking density. As a result, the mechanical properties tend to be improved.

(Partial structure (1))

In the above formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² , R ³ , R ⁵ and R ⁶ each independently represents an alkylene group which may have a substituent.
R ⁴ represents an n + 1 valent linking group.
R ⁷ represents an alkylene group that may have a substituent, an alkenylene group that may have a substituent, or an aromatic ring group that may have a substituent.
l and m each independently represents an integer of 0 to 12.
n represents an integer of 3 or more. * Represents a bond.

^{(R 2, R 3, R} 5 and R ⁶⁾
In the formula (I), R ² , R ³ , R ⁵ and R ⁶ each independently represents an alkylene group which may have a substituent.
The alkylene group may be linear, branched, cyclic, or a combination thereof. Although the carbon number is not particularly limited, it is usually 1 or more, usually 8 or less, preferably 6 or less, more preferably 4 or less, and further preferably 2 or less. There exists a tendency for compatibility with another component to become favorable by setting it as the said upper limit or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a cyclohexylene group. From the viewpoint of compatibility with other components, a methylene group or an ethylene group is preferable, and a methylene group is more preferable. .

  Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. From the viewpoint of ease of synthesis, It is preferably unsubstituted.

(R ⁴ )
In the general formula (I), R ⁴ represents an n + 1 valent linking group. The chemical structure of the n + 1 valent linking group is not particularly limited, and examples thereof include an n + 1 valent hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group from the viewpoint of developability. Moreover, the carbon-carbon single bond in the hydrocarbon group may be interrupted with at least one selected from the group consisting of —O—, —CO— and —NH—.

  Specific examples of the n + 1 valent linking group include the following. * In the chemical formula represents a bond.

(R ⁷⁾
In the formula (I), R ⁷ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent. Represents.

The alkylene group for R ⁷ may be linear, branched, cyclic, or a combination thereof. Although the carbon number is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less, more preferably 4 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexylene group, and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.

  Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

The alkenylene group for R ⁷ may be linear, branched, cyclic, or a combination thereof. Although the carbon number is not particularly limited, it is usually 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferable, and an ethenylene group is more preferable.

  Examples of the substituent that the alkenylene group may have include an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

Examples of the divalent aromatic ring group for R ⁷ 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, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less, and more preferably 10 or less. Particularly preferred. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include 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, and azulene ring. That.
Among the divalent aromatic ring groups, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable from the viewpoint of photocurability.

  Examples of the substituent that the divalent aromatic ring group may have include an alkyl group, an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. . Among these, unsubstituted is preferable from the viewpoint of curability.

Among these, from the viewpoint of curability, R ⁷ is preferably an alkylene group which may have a substituent, more preferably an unsubstituted alkylene group, and even more preferably an ethylene group.

(L and m)
In the said general formula (I), l and m represent the integer of 0-12 each independently. From the viewpoint of development adhesion, it is preferably 0 or more, more preferably 1 or more, and from the viewpoint of curability, it is preferably 8 or less, more preferably 6 or less. The following is more preferable, and 2 or less is particularly preferable. On the other hand, it is preferably 0 from the viewpoint of curability.

(N)
In the general formula (I), n represents an integer of 3 or more. n is preferably 4 or more, more preferably 5 or more, and is preferably 10 or less, more preferably 8 or less, still more preferably 7 or less, and particularly preferably 6 or less. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.

(Partial structure (2))
The epoxy (meth) acrylate resin (b1-A) preferably has a partial structure (2) represented by the following general formula (II) from the viewpoint of development solubility.

In the above formula (II), R ⁸ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an aromatic ring group which may have a substituent. * Represents a bond.

(R ⁸⁾
In the formula (II), R ⁸ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent. Represents.

The alkylene group for R ⁸ may be linear, branched, cyclic, or a combination thereof. Although the carbon number is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexylene group, and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.

  Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

The alkenylene group for R ⁸ may be linear, branched, cyclic, or a combination thereof. Although the carbon number is not particularly limited, it is usually 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferable, and a cyclohexenylene group is more preferable.

  Examples of the substituent that the alkenylene group may have include an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

Examples of the divalent aromatic ring group for R ⁸ 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, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less, and more preferably 10 or less. Particularly preferred. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include 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, and azulene ring. That. Among these, from the viewpoint of photocurability, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

  Examples of the substituent that the divalent aromatic ring group may have include an alkyl group, an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. . Among these, unsubstituted is preferable from the viewpoint of curability.

Among these, from the viewpoint of curability, R ⁸ is preferably an alkenylene group which may have a substituent, more preferably an unsubstituted alkenylene group, and further preferably a cyclohexenylene group. preferable.

  Specific examples of the partial structure (2) represented by the formula (II) include the following. * In the chemical formula represents a bond.

(Partial structure (3))
Moreover, it is preferable that an epoxy (meth) acrylate-type resin (b1-A) has a partial structure (3) represented by the following general formula (III) from a sclerosing | hardenable viewpoint.

In the above formula (III), R ⁹ represents an epoxy resin residue. p represents an integer of 1 or more. * Represents a bond.

(R ⁹ )
In the above formula (III), R ⁹ represents an epoxy resin residue. The epoxy resin residue means a residue obtained by removing an epoxy group from an epoxy resin.
Here, the epoxy resin has the same meaning as described above.

(P)
In the formula (III), p represents an integer of 1 or more. From the viewpoint of achieving both curability and development solubility, p is preferably 2. On the other hand, from the viewpoint of curability, p is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, and 20 or less from the viewpoint of development solubility. Is preferably 15 or less, and more preferably 12 or less. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.

(Partial structure (3-1))
The partial structure (3) represented by the general formula (III) is preferably a partial structure (3-1) represented by the following general formula (III-1) from the viewpoint of development solubility.

  In said formula (III-1), (gamma) represents a bivalent coupling group. The benzene ring in formula (III-1) may be further substituted with an arbitrary substituent. * Represents a bond.

(Γ)
In the formula (III-1), γ represents a divalent linking group. Examples of the divalent linking group include a single bond, an alkylene group which may have a substituent, —CO— or —SO ₂ — from the viewpoint of development solubility.
The alkylene group may be linear, branched, cyclic, or a combination thereof. Although the carbon number is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, a heptylene group, an octylene group, and a dodecylene group. From the viewpoint of curability, a methylene group or a propylene group is preferable. Preferably, a propylene group is more preferable.

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (—F, —Cl, —Br, —I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.
When it has a substituent, the number is not limited and may be 1 or 2 or more.

In addition, when both of the two hydrogen atoms of the methylene group (—CH ₂ —) in the alkylene group are substituted with a substituent, the two substituents may be connected to form a hydrocarbon ring. Good. Specific examples of γ in that case include a group represented by the following formula (IV) and a group represented by the following formula (V). * In the chemical formula represents a bond.

  Examples of the optional substituent that the benzene ring in formula (III-1) 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. Is mentioned. The number of substituents is not particularly limited, either one or two or more. Moreover, when the benzene ring in the said formula (III-1) has a substituent, the two benzene rings in a formula (III-1) may be connected by this substituent.

  Among these, from the viewpoint of curability, γ is preferably an alkylene group which may have a substituent, more preferably an unsubstituted alkylene group, and even more preferably a propylene group.

(Partial structure (3-2))
The partial structure (3) represented by the general formula (III) is preferably a partial structure (3-2) represented by the following general formula (III-2) from the viewpoint of curability.

  The benzene ring in the above formula (III-2) may be further substituted with an arbitrary substituent. * Represents a bond.

  As an arbitrary substituent which the benzene ring in the said formula (III-2) may have, a hydroxyl group, an alkyl group, an alkoxy group etc. are mentioned, for example. The number of substituents is not particularly limited, either one or two or more. Among these, from the viewpoint of development adhesion, an alkyl group is preferable, a cycloalkyl group is more preferable, and an adamantyl group is more preferable.

(Partial structure (3-3))
The partial structure (3) represented by the general formula (III) preferably includes a partial structure (3-3) represented by the following general formula (III-3) from the viewpoint of curability.

In the above formula (III-3), R ¹⁰ represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (III-3) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ¹⁰ )
In the formula (III-3), R ¹⁰ 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, cyclic, and combinations thereof. Among these, a linear one is preferable from the viewpoint of development solubility, while a cyclic one is preferable from the viewpoint of development adhesion. 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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

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 curability.
Specific examples of the divalent branched aliphatic group include a divalent linear aliphatic group as described above, a side chain with a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. And a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
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 10 or less and 5 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms are removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. It is done. 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; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxyl group. 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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
Among these, from the viewpoint of photocurability, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences 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 curability.

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. There exists a tendency for sclerosis | hardenability to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for sclerosis | hardenability to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the following formulas (III-3-A) to (III-3-E). And the like. Among these, a group represented by the following formula (III-3-A) is preferable from the viewpoint of development solubility. * In the chemical formula represents a bond.

As described above, the benzene ring in formula (III-3) 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 curability.

(Partial structure (3-4))
The partial structure (3) represented by the general formula (III) preferably includes a partial structure (3-4) represented by the following general formula (III-4) from the viewpoint of curability.

  In said formula (III-4), (gamma) represents a bivalent coupling group. The benzene ring in formula (III-4) may be further substituted with an arbitrary substituent. * Represents a bond.

As γ in the formula (III-4), those described as γ in the formula (III-1) can be preferably employed.
Moreover, as an arbitrary substituent which the benzene ring in the said formula (III-4) may have, as an arbitrary substituent which the benzene ring in the said formula (III-1) may have, What has been described can be preferably employed.

  The epoxy (meth) acrylate resin (b1-A) has a partial structure (3-1) from the viewpoint of development solubility among the partial structures (3-1) to (3-4). Is preferred.

  As a specific method for producing the epoxy (meth) acrylate resin (b1-A), a method described in JP-A-2007-119718 can be employed.

  Moreover, as an epoxy (meth) acrylate resin, from the viewpoint of curability, an epoxy (meth) acrylate resin (b1-B) having a partial structure represented by the following formula (i) (hereinafter referred to as “epoxy (meth) acrylate” ) -Based resin (b1-B) ”and epoxy (meth) acrylate-based resin (b1-C) having a partial structure represented by the following general formula (ii) (hereinafter referred to as“ epoxy ( (Meth) acrylate-based resin (b1-C) ”may be abbreviated.). Further, from the viewpoint of reliability, epoxy (meth) acrylate resin (b1-C) is more preferable.

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

In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.

(R ^b )
In the formula (i), R ^b 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, cyclic, and combinations thereof. Among these, a linear one is preferable from the viewpoint of development solubility, while a cyclic one is preferable from the viewpoint of development adhesion. 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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

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 curability.
Specific examples of the divalent branched aliphatic group include a divalent linear aliphatic group as described above, a side chain with a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. And a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
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 10 or less and 5 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms are removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. It is done. 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; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxyl group. 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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. Among these, from the viewpoint of photocurability, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences 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 curability.

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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for sclerosis | hardenability to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  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 (i-A) to (i-E), etc. Is mentioned. Among these, from the viewpoint of development solubility, a group represented by the following formula (i-A) is preferable. * In the chemical formula represents a bond.

As described above, the benzene ring in formula (i) 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 curability.

  Moreover, it is preferable that the partial structure represented by the said general formula (i) is a partial structure represented by the following general formula (i-1) from a sclerosing | hardenable viewpoint.

In formula (i-1), R ^a and R ^b have the same meaning as in formula (i). R ^X represents a hydrogen atom or a polybasic acid residue. * Represents a bond. The benzene ring in formula (i-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, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid. An acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, or biphenyltetracarboxylic acid.

The partial structure represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (b1-B) may be one type or two or more types. For example, R ^X is a hydrogen atom. And those in which R ^X is a polybasic acid residue may be mixed.

  The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (b1-B) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable and 15 or less is more preferable. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.

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

(R ^d )
In the formula (ii), R ^d 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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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 the like. Among these, an adamantane ring is preferable from the viewpoint of reliability.

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, 5 or less, and more preferably 4 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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, cyclic, and combinations thereof. Among these, a linear one is preferable from the viewpoint of compatibility, while a cyclic one is preferable from the viewpoint of reliability. 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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

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 curability.
Specific examples of the divalent branched aliphatic group include a divalent linear aliphatic group as described above, a side chain with a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. And a structure having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms are removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. It is done. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of reliability.

  Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxyl group. 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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
Among divalent aromatic ring groups, from the viewpoint of patterning properties, a benzene ring having two free valences, a naphthalene ring having two free valences, or a fluorene ring having two free valences are preferred, A fluorene ring having two free valences is more preferred.

  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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

  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 (iA) to (iE), etc. Is mentioned. Among these, the group represented by the formula (i-C) is preferable from the viewpoint of reliability.

  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.

  Moreover, it is preferable that the partial structure represented by said formula (ii) is a partial structure represented by the following formula (ii-1) from a compatible viewpoint.

In formula (ii-1), R ^c has the same meaning as in formula (ii). R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ^α )
In the formula (ii-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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 the like. Among these, an adamantane ring is preferable from the viewpoint of compatibility.

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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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 reliability.

  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, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  n represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

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

As described above, the benzene ring in formula (ii-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 (ii-1) are given below.

  Moreover, it is preferable that the partial structure represented by the said general formula (ii) is a partial structure represented by the following general formula (ii-2) from a viewpoint of reliability.

In formula (ii-2), R ^c has the same meaning as in formula (ii). ^Rβ represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ^β )
In the formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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 the like. Among these, an adamantane ring is preferable from the viewpoint of compatibility.

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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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. There exists a tendency for image development adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.
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 reliability.

  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, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.

Among these, from the viewpoint of compatibility, 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 reliability, 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 (ii-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. In addition, two benzene rings in formula (ii-2) may be linked via these substituents.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.

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

  On the other hand, the partial structure represented by the general formula (ii) is preferably a partial structure represented by the following general formula (ii-3) from the viewpoint of compatibility.

In formula (ii-3), R ^c and R ^d have the same meaning as in formula (ii). 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 (ii-3), that is, a plurality of formulas (ii-3) are connected 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, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid. An acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, or biphenyltetracarboxylic acid.

The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (b1-C) may be one type or two or more types. For example, R ^X is a hydrogen atom. And those in which R ^Z is a polybasic acid residue may be mixed.

  The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (b1-C) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further more preferable. When it is at least the lower limit value, the curability tends to be good, and when it is at most the upper limit value, the development solubility tends to be good.

Epoxy (meth) acrylate resin (b1) may be used individually by 1 type, or may mix and use 2 or more types of resin.
Moreover, you may replace and use a part of above-mentioned epoxy (meth) acrylate type resin (b1) for another binder resin. That is, you may use together an epoxy (meth) acrylate type resin (b1) and another binder resin. In this case, the proportion of the epoxy (meth) acrylate resin (b1) in the alkali-soluble resin (b) is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more. More preferably, it is more preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more. Moreover, it is preferable to set it as 90 mass% or less, It is more preferable to set it as 80 mass% or less, It is more preferable to set it as 70 mass% or less, It is especially preferable to set it as 60 mass% or less.

  There is no restriction | limiting in the other binder resin which can be used together with an epoxy (meth) acrylate type resin (b1), What is necessary is just to select from resin normally used for the photosensitive coloring composition. Examples thereof include binder resins described in JP 2007-271727 A, JP 2007-316620 A, JP 2007-334290 A, and the like. In addition, from the viewpoint of reliability and surface smoothness, (meth) acrylic copolymer resins described in International Publication No. 2017/110893 are preferable. In addition, all other binder resins may be used alone or in combination of two or more.

  Moreover, it is preferable to use (b2) acrylic resin as (b) alkali-soluble resin from a compatible viewpoint with a coloring agent, a dispersing agent, etc.

As the acrylic resin, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylenic monomers. A copolymer with an unsaturated monomer (hereinafter referred to as “unsaturated monomer (b2-2)”) can be exemplified.
Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid , Unsaturated dicarboxylic acids such as citraconic acid, citraconic anhydride, mesaconic acid or the like; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids having two or more valences such as ω-carboxypolycaprolactone mono (meth) acrylate, etc. ) Acrylate; p-vinylbenzoic acid and the like.
These unsaturated monomers (b2-1) can be used individually or in mixture of 2 or more types.

  Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy- aromatic vinyl compounds such as α-methylstyrene, p-vinylbenzylglycidyl 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 and 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 (b2-2) can be used individually or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 It is -50 mass%, More preferably, it is 10-40 mass%. By copolymerizing the unsaturated monomer (b2-1) in such a range, there is a tendency that a photosensitive coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, JP-A-7-140654 and JP-A-8-259876. It is disclosed in Kaihei 10-31308, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Can be mentioned.
The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method. For example, JP 2003-222717 A, JP The structure, Mw, and Mw / Mn can be controlled by the methods disclosed in Japanese Patent Application Publication No. 2006-259680, International Publication No. 2007/029871, and the like.

<(C) Photopolymerization initiator>
(C) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. 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, and N-aryl-α-amino acids described in JP-A-10-39503 Salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester compounds described in JP 2000-80068 A, JP 2006-36750 A, etc. Etc.

  Specifically, for example, as a metallocene compound, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl) ), Dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium di ( 2,6-difluorophenyl), dicyclopentadienyl titanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), Di (methylcyclopentadienyl) titanium bis (2,6-difluoro Eniru), dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like.

  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, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

  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) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  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. Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in the structure, so they are highly sensitive in a small amount and stable against thermal reactions. It is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.

  Examples of the oxime ester compound include compounds represented by the following general formula (IV).

In the above formula (IV), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents an arbitrary substituent containing an aromatic ring.
R ^22a represents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent.
n represents an integer of 0 or 1.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. It is. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
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 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl. Group or N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ^21a 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 photosensitive coloring 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 a group in which these substituents are linked. From the viewpoint of properties, an alkyl group, an alkoxy group, or a group in which these are connected is preferable, and a connected alkoxy group is more preferable.
Among these, from the viewpoint of developability, R ^21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having a linked alkoxy group as a substituent. preferable.

R ^21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, or an optionally substituted diphenyl sulfide group. Of these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity.

The number of carbon atoms of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent or sensitivity. 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the substituent may be unsubstituted. Is preferred.

The number of carbon atoms of the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent or sensitivity. 10 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl 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 ease of synthesis, it is preferably unsubstituted. .
Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and further preferably an acetyl group.

  In addition, the initiator described in JP-A-2006-133574 is also preferably used from the viewpoint that the contamination of the liquid crystal layer by the colorant is reduced.

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. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarins having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. Dyes, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A-47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Examined Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005. JP, 59-56403, JP 2-69, JP 57-168888, JP 5-107761. JP-5-210240 discloses, mention may be made of 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 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) Ethylenically unsaturated compound>
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (D) Sensitivity improves by including an ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound 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 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less. There exists a tendency for it to become high sensitivity by setting it as the said lower limit or more, and there exists a tendency for the solubility to a solvent to improve by setting it as the said upper limit or less. As a combination of the upper limit and the lower limit, for example, 2 to 8 are preferable, 4 to 7 are more preferable, and 5 to 7 are more preferable.
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 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV -7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

Among these, from the viewpoint of curability, it is preferable to use (meth) acrylic acid alkyl ester as (d) ethylenically unsaturated compound, and it is more preferable to use dipentaerythritol hexaacrylate.
These may be used alone or in combination of two or more.

<(E) Solvent>
The photosensitive coloring composition of the present invention may contain (e) a solvent. (E) By containing a solvent, a pigment can be disperse | distributed in a solvent and there exists a tendency for application | coating to become easy.
The photosensitive coloring composition of the present invention is usually used as needed (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound. Various other components are used in a state dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferable from the viewpoints of dispersibility and coatability.

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

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-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl Ether, tri Chi glycol monoethyl 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 colored spacer by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. 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. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the photosensitive coloring composition obtained later tends to decrease. 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 photosensitive coloring 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 foreign matter defects due to precipitation and solidification of a colorant 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.

  When a high boiling point solvent is used in combination, 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. preferable. By setting it to the lower limit value or more, for example, there is a tendency that colorants and the like are precipitated and solidified at the tip of the slit nozzle to cause a foreign matter defect, and by setting the lower limit value or less, the drying temperature of the composition Is suppressed, and there is a tendency that problems such as a tact defect in the reduced-pressure drying process and a pin mark of prebaking can be suppressed.

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>
The photosensitive coloring composition of the present invention may contain (f) a dispersant for the purpose of (a) finely dispersing the colorant and stabilizing the dispersion state.
(F) As the dispersant, a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxyl group; a phosphate group; a sulfonate group; or a base thereof; primary, secondary or tertiary A polymeric dispersant having a functional group such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable. In particular, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, disperses the pigment. In particular, it is particularly preferable from the viewpoint that it can be dispersed with a small amount of a dispersant.

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine 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 Corp.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like.
These polymer dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Among these, from the viewpoint of the dispersibility of the pigment, (f) the dispersant preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group. It is particularly preferable to include it.
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.

Examples of urethane-based and acrylic polymer dispersants include DISPERBYK160 to 166, 182 series (all are urethane-based), DISPERBYK2000, 2001, BYK-LPN21116 (all are acrylic-based) (all manufactured by BYK Chemie). .
If a chemical structure preferable as a urethane-based polymer dispersant is specifically exemplified, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000, molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting an active hydrogen with a compound having a tertiary amino group. 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 Aliphatic 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 molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds has 1 carbon atom. Examples thereof include those alkoxylated with ˜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 dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol 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 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 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 active hydrogen and tertiary amino group in the 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 can be mentioned.

  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 when producing the urethane-based polymer dispersant is 10 to 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule with respect to 100 parts by mass of the polyisocyanate compound. 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, 0.2 to 25 parts by mass of a compound having an active hydrogen and a tertiary amino group in the molecule, preferably 0.3 to 24 Part 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 an active hydrogen and a tertiary amino group in the 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 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, a decrease in developability tends to be suppressed.

In addition, when an isocyanate group remains in a polymer dispersing agent by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time increases.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Dispersibility and dispersion stability tend to be good when the lower limit is exceeded, and lowering of solubility and dispersibility tends to be easily suppressed when the upper limit is reached.

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

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monomer having no functional 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-cyclohe N-substituted maleimides such as silmaleimide, 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 functional group and a B block having no functional group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may contain a partial structure derived from the unsaturated group-containing monomer not containing the functional group. May be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the content rate 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 is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but a partial structure derived from two or more types of monomers is contained in one B block. 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, more preferably 5/95 to 60/40 (mass ratio), and within this range, a balance between dispersibility and storage stability can be ensured. Tend.
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 dispersibility by making it in the range.

In addition, in such a block copolymer, an amino group generated in the production process may be usually contained, but the amine value is about 1 to 100 mgKOH / g, from the viewpoint of dispersibility, Preferably it is 10 mgKOH / g or more, More preferably, it is 30 mgKOH / g or more, More preferably, it is 50 mgKOH / g or more, Preferably it is 90 mgKOH / g or less, More preferably, it is 80 mgKOH / g or less, More preferably, it is 75 mgKOH / g or less.
Here, the amine value of the dispersant such as these block copolymers is expressed 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. ]
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. There exists a tendency which can ensure favorable dispersibility by setting it as the said range.

  When the acrylic polymer dispersant has a quaternary ammonium base as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is represented by the following formula (i). It is preferable to have a repeating unit (hereinafter sometimes referred to as “repeating 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 either 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 phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group and a phenylethyl group Group, a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl 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. And R ³² is preferably a phenylmethyl group or a phenylethyl group, more preferably R ³¹ and R ³³ are a methyl group, and R ³² is a phenylmethyl group.

  When the acrylic polymer dispersant has a tertiary amino group as a functional 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 single 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 ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more from the viewpoint of dispersibility, and 5 mol. % Or more, more preferably 10 mol% or more, more preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. Is more preferable, and it is especially preferable that it is 15 mol% or less.

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

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

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 either 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 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 even more 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.

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

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 either 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 phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenyl group It is preferably a butyl group, more preferably a phenylmethyl group or a phenylethyl group.

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 phenylmethyl 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 polymer dispersant is preferably 30 mol% or more and 40 mol% or more from the viewpoint of dispersibility. More preferably, it is more preferably 50 mol% or more, more preferably 80 mol% or less, and even more preferably 70 mol% or less.

  The 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.

  From the viewpoint of further improving dispersibility, the polymer dispersant is composed of an A block having the repeating unit (i) and the repeating unit (ii), and a B block not having the repeating unit (i) and the repeating unit (ii). It is preferable that it is a block copolymer which has these. 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 ratio 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.

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

<Other ingredients of photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes an adhesion improver such as a silane coupling agent, a surfactant (applicability improver), a pigment derivative, a photoacid generator, a crosslinking agent, and a mercapto compound. Additives such as development improvers, ultraviolet absorbers and antioxidants can be appropriately blended.

(1) Adhesion improver The photosensitive coloring 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 phosphoric acid group-containing compound and the like are preferable.
As the kind of the silane coupling agent, various kinds such as epoxy, (meth) acrylic and amino 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 phosphoric acid group-containing compound, (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 compounds may be used singly or in combination of two or more.

(2) Surfactant The photosensitive coloring 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 Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340. (Manufactured by Shin-Etsu Silicone), Megafuck F-470, Megafuck F-475, Megafuck F-478, Megafuck F-554, Megafuck F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray) DS-401 (manufactured by Daikin), L-77 (manufactured by Nihon Unicar), FC4430 (manufactured by 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 photosensitive coloring 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. In this case, the crosslinking reaction proceeds. Among such photoacid generators, those having a high solubility in a solvent, particularly a solvent used in a photosensitive coloring 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, p -Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoroa Senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts and the like, sulfonium organoboron complexes such as 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 A crosslinking agent can be further added to the photosensitive coloring composition of the present invention. 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 , R ⁶⁶ and R ⁶⁷ represent —CH ₂ OR ^68, and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH ₂ OR ^68. R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and the rest of R ⁶⁷ independently of each other represent hydrogen or a —CH ₂ OR ⁶⁸ group, and R ⁶⁸ represents a hydrogen atom or a carbon number of 1-4. Represents an alkyl group.
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 in the total solid of a photosensitive coloring 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 photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content ratio of the (a) colorant is 23% by mass or less in the total solid content of the photosensitive coloring composition. (A) Since the colorant is a component that does not elastically deform, it is considered that the mechanical properties of the colored spacer obtained by setting the content ratio to the upper limit or less are improved.
(A) Although the content rate of a coloring agent will not be specifically limited if it is 23 mass% or less in the total solid of a photosensitive coloring composition, 22 mass% or less is preferable, 20 mass% or less is more preferable, 18 mass% % Or less is more preferable, 16% by mass or less is more preferable, 15% by mass or less is particularly preferable, 14% by mass or less is most preferable, 1% by mass or more is preferable, 5% by mass or more is more preferable, and 8% by mass. % Or more is more preferable, 10 mass% or more is further more preferable, and 12 mass% or more is especially preferable. (A) By making the content rate of a coloring agent below the said upper limit, mechanical characteristics become favorable, sufficient plate-making characteristic is easy to be obtained, and there exists a tendency which is excellent in electrical reliability, Moreover, the said lower limit By setting it as the above, there exists a tendency for sufficient light-shielding property to be acquired.

  The content ratio of the pigment in the photosensitive coloring composition of the present invention is not particularly limited, but is not particularly limited as long as it is 23% by mass or less in the total solid content of the photosensitive coloring composition, but is preferably 22% by mass or less, and 20 % By mass or less is more preferable, 18% by mass or less is more preferable, 16% by mass or less is further more preferable, 15% by mass or less is particularly preferable, 14% by mass or less is most preferable, and 1% by mass or more is preferable. % By mass or more is more preferable, 8% by mass or more is more preferable, 10% by mass or more is further more preferable, and 12% by mass or more is particularly preferable. By making the content ratio of the pigment not more than the above upper limit value, the mechanical characteristics become good, and sufficient plate-making characteristics tend to be obtained, and the electric reliability tends to be excellent, and more than the above lower limit value. Thus, there is a tendency that sufficient light shielding properties can be obtained.

  The content ratio of the yellow pigment in the total solid content of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and further preferably 10% by mass or more. It is particularly preferably at least 50% by mass, more preferably at most 50% by mass, more preferably at most 40% by mass, further preferably at most 35% by mass, further preferably at most 30% by mass, particularly preferably at most 25% by mass, The mass% or less is most preferable. There exists a tendency which can fully suppress the transmittance | permeability of wavelength 400-500 nm by setting it as the said lower limit or more, and there exists a tendency for sufficient plate-making performance to be easy to be obtained by setting it as the said upper limit or less.

  The total content of the red pigment and the orange pigment in the total solid of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and 30% by mass. Or less, more preferably 20% by mass or less, further preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less. When it is at least the lower limit, the optical density (OD) tends to be high, and when it is at most the upper limit, sufficient plate-making performance tends to be obtained.

  The content of the red pigment in the total solid of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and preferably 30% by mass or less, 20% by mass. % Or less is more preferable, 15 mass% or less is more preferable, 10 mass% or less is further more preferable, and 8 mass% or less is especially preferable. When it is at least the lower limit, the optical density (OD) tends to be high, and when it is at most the upper limit, sufficient plate-making performance tends to be obtained.

  The content ratio of the orange pigment in the total solid of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and preferably 30% by mass or less, 20% by mass. % Or less is more preferable, 15 mass% or less is more preferable, 10 mass% or less is further more preferable, and 8 mass% or less is especially preferable. When it is at least the lower limit, there is a tendency that both optical density (OD) and transmittance suppression at a wavelength of 400 to 500 nm tend to be compatible, and when it is not more than the upper limit, sufficient plate-making performance tends to be obtained.

From the viewpoint of color tone, the photosensitive coloring composition preferably has a low content of blue pigment and purple pigment in the total solid, preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. It is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and most preferably 0% by mass, that is, most preferably not contained.
On the other hand, from the viewpoint of light shielding properties, a blue pigment and / or a purple pigment may be included. In that case, the content ratio of the blue pigment and the purple pigment in the total solid content is preferably 1% by mass or more. % By mass or more is more preferable, 8% by mass or more is further preferable, 10% by mass or more is particularly preferable, 15% by mass or more is most preferable, 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass. % Or less is more preferable. There exists a tendency for sufficient light-shielding property to be acquired by setting it as the said lower limit or more, and there exists a tendency which can obtain the color tone close | similar to black by setting it as the said upper limit or less.

  (B) The content rate of alkali-soluble resin is 5 mass% or more normally in the total solid of the photosensitive coloring composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more, More preferably, it is 30 mass. % Or more, particularly preferably 35% by weight or more, and usually 85% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, still more preferably 60% by weight or less, and even more preferably 50% by weight or less. Especially preferably, it is 45 mass% or less. (B) By making the content rate of alkali-soluble resin more than the said lower limit, there exists a tendency for mechanical characteristics to become favorable and for developability to become favorable. Moreover, by setting it as the said upper limit or less, there exists a tendency which can maintain appropriate sensitivity, can suppress the melt | dissolution by the developing solution of an exposure part, and can suppress the fall of adhesiveness.

  (C) The content ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more in the total solid content of the photosensitive coloring composition of the present invention. More preferably, it is 2% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less, and particularly preferably 5% by mass or less. (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 the fall of the solubility with respect to the developing solution of an unexposed part is suppressed 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, usually 10% by mass in the total solid content of the photosensitive coloring composition of the present invention. %, Preferably 5% by mass or less, and the polymerization accelerator is usually used in a proportion of 0.1 to 50 parts by mass and 0.1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (c). It is preferable. 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.
Moreover, when using a sensitizing dye with (c) a photoinitiator, the content rate of a sensitizing dye is 20 mass% or less normally in the total solid in a photosensitive coloring composition from a viewpoint of a sensitivity, Preferably Is 15% by mass or less, more preferably 10% by mass or less.

  (D) The content of the ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably, in the total solid content of the photosensitive coloring composition of the present invention. It is 20% by mass or more, particularly preferably 30% by mass or more, and is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. (D) By maintaining the content ratio of the ethylenically unsaturated compound at or above the lower limit value, it is possible to maintain appropriate sensitivity, suppress dissolution by the developer in the exposed area, and to suppress decrease in adhesion, Further, by setting the amount to be equal to or less than the upper limit value, it is possible to suppress an increase in the permeability of the developer to the exposed portion and to easily obtain a good image.

  On the other hand, the content ratio of (b) alkali-soluble resin with respect to 100 parts by mass of (d) ethylenically unsaturated compound is not particularly limited, but is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and 100 parts by mass or more. More preferably, it is usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and further preferably 300 parts by mass or less. When the value is not less than the lower limit value, there is a tendency that an appropriate development state without peeling or the like is obtained, and when the value is not more than the upper limit value, there is a tendency that an appropriate dissolution time can be obtained with respect to the developer. Moreover, as a combination of an upper limit and a minimum, for example, 50-700 mass parts is preferable, 80-500 mass parts is more preferable, 80-400 mass parts is further more preferable, 100-300 mass parts is mentioned especially preferable.

  In addition, the photosensitive coloring composition of this invention uses the (e) solvent, and the content rate of the total solid content is 5 mass% or more normally, Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more. In addition, the liquid is usually adjusted to 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less.

  When the photosensitive coloring composition of this invention contains (f) a dispersing agent, the content rate of (f) dispersing agent is 1 mass% or more normally in the total solid of a photosensitive coloring composition, and 2 mass% or more. Moreover, 30 mass% or less and 20 mass% or less are preferable normally, 15 mass% or less is more preferable, 10 mass% or less is further more preferable, and 5 mass% or less is especially preferable. (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.

In addition, the content ratio of the (f) dispersant to (a) 100 parts by mass of the 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. It is preferable that it is 30 mass parts or less. (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 improver, the content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 4% by total solid content in the photosensitive coloring composition. 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 in the total solid in a photosensitive coloring composition, Preferably it is 0.005-1 mass%, More preferably, it is 0.00. It is 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 photosensitive coloring composition>
The photosensitive coloring composition of this invention can be used conveniently for colored spacer formation. From the viewpoint of use as a colored spacer, it is preferable that the cured film has a higher optical density (OD) per 1 μm. The colored spacer alone obtained by curing the photosensitive coloring composition of the present invention is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more. 0.08 or more is more preferable, 0.10 or more is particularly preferable, and 0.15 or more is most preferable. Here, the optical density (OD) per 1 μm of film thickness is a value measured by the method described in Examples described later.

  Further, when laminated with a blue color filter layer, the optical density (OD) of the two layers obtained by laminating a colored spacer and a blue color filter layer is preferably 0.5 or more, and 1.0 or more. It is more preferable. Here, the optical density (OD) of the two laminated layers is a value measured by the method described in Examples described later.

  In the photosensitive coloring composition of the present invention, the ratio of the average absorbance at a wavelength of 400 to 500 nm to the average absorbance at a wavelength of 500 to 700 nm is preferably 3.0 or more, more preferably 4.0 or more, and 5.0. The above is more preferable, and 6.0 or more is particularly preferable. Moreover, it is preferable that it is 15.0 or less, 13.0 or less is more preferable, 11.0 or less is further more preferable, 9.0 or less is especially preferable. By setting it to the lower limit value or more, a color tone close to black can be obtained when laminated with a blue color filter layer, and the transmittance of 400 to 500 nm tends to be suppressed. Moreover, there exists a tendency which can make optical density (OD) high by setting it as the said upper limit or less.

Here, the ratio of the average absorbance at a wavelength of 400 to 500 nm to the average absorbance at a wavelength of 500 to 700 nm of the photosensitive coloring composition forms a cured film having a thickness of 2.5 μm using the photosensitive coloring composition, It can be specified by measuring the absorbance at a wavelength of 400 to 700 nm every 1 nm with a spectrophotometer.
Although detailed measurement conditions etc. are not specifically limited, For example, it can measure with the following method.
First, a photosensitive coloring composition is applied onto a glass substrate (“AN100” manufactured by AGC) using a spinner. Next, a coating film is formed by heating and drying on a hot plate at 90 ° C. for 90 seconds. The obtained coating film is irradiated with ultraviolet rays under air. Intensity at a wavelength of 365nm is used ultraviolet is 32 mW / cm ^2, amount of exposure to 70 mJ / cm ^2. Subsequently, a developer comprising an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used, and the water pressure was 0 at 25 ° C. After 15 MPa shower development, development is stopped with pure water and washed with water spray. The shower development time is adjusted between 10 and 120 seconds and is 1.5 times as long as the unexposed coating film is dissolved and removed. The solid film substrate obtained by these operations is heated in an oven at 230 ° C. for 20 minutes to cure the pattern, thereby obtaining a substrate with a cured film having a thickness of 2.5 μm. Next, the absorbance at a wavelength of 400 to 700 nm of the substrate is measured every 1 nm using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation as a contrast to a glass substrate not coated with the photosensitive coloring composition. The average absorbance is calculated by averaging the measured values of the absorbance every other nm of the wavelength 400 to 500 nm, the average absorbance of the wavelength 500 to 700 nm is similarly calculated, and the average of the wavelength 400 to 500 nm with respect to the average absorbance of the wavelength 500 to 700 nm Calculate the absorbance ratio.

  In addition, the photosensitive coloring composition of the present invention is used for forming a colored spacer, particularly for a liquid crystal display having a structure in which a blue color filter layer is provided on the opposite side of the colored spacer in the frame portion. When it is used, the color tone is preferably close to black when superimposed on the blue color filter layer, and the color tone is preferably x ≧ 0.20 and y ≧ 0.20, more preferably x ≧ 0. More preferably, 25 and y ≧ 0.25. This color tone can be measured by the procedure described in the examples.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition of this invention is manufactured in accordance with 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 coating characteristics of the photosensitive coloring composition are improved.

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

In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive coloring composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system that does not contain (c) a photopolymerization initiator and (d) an ethylenically unsaturated compound.
When (a) the colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle 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 tends to vary depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like, and may be adjusted as appropriate. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) is in the range of 50 to 300 when the pigment dispersion or the photosensitive coloring composition is applied to the substrate. By setting it to the above lower limit value or more, the dispersion treatment is not sufficient and the remaining of the rough pigment ((a) colorant) particles can be suppressed, and the developability, adhesion, resolution, etc. tend to be sufficient. . Moreover, by setting it as the said upper limit or less, there exists a tendency which can suppress that a pigment crushes and many ultrafine particles generate | occur | produce and can make dispersion stability favorable.

Further, the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm. The particle size is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the photosensitive coloring composition to obtain a uniform solution. In the manufacturing process of the photosensitive coloring composition, fine dust is often mixed in the liquid. Therefore, the obtained photosensitive coloring composition is preferably filtered through a filter or the like.

[Cured product]
The cured product of the present invention can be obtained by curing the photosensitive coloring composition of the present invention. A cured product obtained by curing the photosensitive coloring composition can be suitably used as a colored spacer.

[Coloring spacer]
The colored spacer of the present invention composed of the cured product of the present invention will be described in accordance with its production method.

(1) Support As long as the support for forming the colored spacer has an appropriate strength, the material thereof is not particularly limited. Transparent substrates are mainly used. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, sheets made of thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy. Examples thereof include thermosetting resin sheets such as resins, unsaturated polyester resins, 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) Colored spacer The photosensitive colored composition of the present invention can be used in the same applications as known photosensitive colored compositions for color filters. The method will be described.

  Usually, a photosensitive coloring composition is supplied in a film shape or a pattern shape by a method such as coating on a support on which a coloring spacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as exposure-development photolithography. Then, a colored spacer is formed on the support by performing additional exposure or thermosetting treatment as necessary.

(3) Formation of colored spacer [1] Supplying method to substrate The photosensitive colored composition of the present invention is usually supplied onto a support in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as 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 can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method. Above all, the die coating method reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. It is preferable from the viewpoint.

  The coating amount varies depending on the application. For example, in the case of a colored spacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, display spots or the like may occur on the liquid crystal panel.

  However, when the colored spacers having different heights are collectively formed by the photolithography method using the photosensitive coloring composition of the present invention, the finally formed colored spacers have different heights.

  Note that a known substrate such as a glass substrate can be used as the support. The substrate surface is preferably a flat surface.

[2] Drying method The drying after supplying the photosensitive coloring composition onto the support is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.

  Drying conditions such as drying temperature and drying time can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. Usually, it is selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably in the range of 30 seconds to 3 minutes at a temperature of 50 ° C. to 110 ° C.

[3] Exposure Method Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating with an ultraviolet light source or a visible light source through this mask pattern. When exposure is performed using an exposure mask, the exposure mask is placed close to the coating film of the photosensitive coloring composition, or the exposure mask is arranged at a position away from the coating film of the photosensitive coloring composition. A method of projecting exposure light through a 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, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure is performed in a deoxygenated atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.

As a preferred embodiment of the present invention, when colored spacers having different heights are simultaneously formed by photolithography, for example, a light shielding part (light transmittance 0%) and a plurality of openings have the highest average light transmittance. An exposure mask having an opening (fully transmissive opening) and an opening having a low average light transmittance (intermediate transmissive opening) is used. By this method, a difference in the residual film ratio is caused by a difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, a difference in exposure amount.
For example, a method of creating the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known. Also known is a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.

  The light source used for said 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 laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared 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 the 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.

Energy of exposure generally, 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 target 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.

[4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, 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; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; 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 can 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.

[5] Additional exposure and thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above exposure method, if necessary, or may be subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature ranges from 100 ° C. to 280 ° C., preferably from 150 ° C. to 250 ° C., and the time ranges from 5 minutes to 60 minutes.

  The size and shape of the colored spacer of the present invention are appropriately adjusted depending on the specifications of the color filter to which the colored spacer is applied, but the photosensitive colored composition of the present invention is particularly suitable for the height of the spacer and the sub-spacer by photolithography. It is useful in simultaneously forming colored spacers having different thicknesses. In this case, the height of the spacer is usually about 2 to 7 μm, and the sub-spacer is usually about 0.2 to 1.5 μm lower than the spacer. Have.

[Color filter]
The color filter of the present invention is provided with the colored spacer of the present invention as described above. For example, on a glass substrate as a transparent substrate, a black matrix, a red, green, and blue pixel coloring layer, and an overcoat layer Are stacked to form a colored spacer, and then an alignment film is formed. Alternatively, the pixel coloring layer and the coloring spacer may be formed on the liquid crystal driving side substrate, or may be separately formed on the transparent substrate and the liquid crystal driving side substrate.
In addition, as described in Korean Published Patent No. 10-2013-0015734, Korean Published Patent No. 10-2015-0059026, Korean Published Patent No. 10-2017-0017447, colored spacers are formed in the non-display area. In this case, by laminating a color filter of a blue layer or a red layer on the opposite side, light leakage to the non-display area can be reduced. Further, only the blue layer, only the red layer, and only the green layer are possible. A liquid crystal display having an LED backlight tends to have a strong blue light component of the LED. For this reason, blue light components are easily transmitted. For example, in the case of only a single layer, particularly only a blue layer, light leakage at a wavelength of 400 to 500 nm tends to occur. This light leakage can be adjusted by the laminated structure when the liquid crystal display is used, or the material characteristics of the opposed colored spacer. For example, a colored spacer obtained by curing the photosensitive coloring composition of the present invention can be used. Is preferred.

[Image display device]
The image display device of the present invention includes the colored spacer of the present invention.
For example, a liquid crystal cell is formed by laminating the color filter having the colored spacer of the present invention described above and a liquid crystal driving side substrate, and the liquid crystal is injected into the formed liquid crystal cell, thereby providing the colored spacer of the present invention. The image display device of the present invention such as a liquid crystal display device can be manufactured.

EXAMPLES Next, although an Example, a comparative example, and a reference 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 photosensitive coloring composition used in the following examples, comparative examples and reference examples are as follows.

<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 the mixture was further stirred 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 8400, and the acid value was 80 mgKOH / g.

<Alkali-soluble resin-II>
A mixture of 210.1 parts by mass of propylene glycol monomethyl ether acetate and 52.5 parts by mass of propylene glycol monomethyl ether was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Here, 3.52 parts by mass of benzyl methacrylate, 68.8 parts by mass of methacrylic acid, 39.7 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2′-azobis-2- A mixed solution of 3.3 parts by mass of methylbutyronitrile was dropped over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 38.4 parts by mass of glycidyl methacrylate, 0.8 part by mass of trisdimethylaminomethylphenol and 0.1 part by mass of hydroquinone were added, and the reaction was continued at 100 ° C. for 12 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the alkali-soluble resin-II thus obtained was 19100, and the acid value was 198 mgKOH / g.

<Alkali-soluble resin-III>
17 parts by mass of succinic anhydride and 350 parts by mass of dipentaerythritol polyacrylate (A-9550 manufactured by Shin-Nakamura Chemical Co., Ltd.), 1.8 parts by mass of triethylamine, 0.12 parts by mass of 4-methoxyphenol, and propylene glycol monomethyl ether acetate By reacting at 85 ° C. for 6 hours in the presence of 91.8 parts by mass, a polyfunctional acrylate (d-1) having one carboxyl group and two or more acryloyl groups in one molecule was obtained.
Subsequently, 32.7 g of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. jER-828, epoxy equivalent 186), 460.7 g of the polyfunctional acrylate (d-1), 2,2,6,6-tetramethylpiperidine 1 -0.2 g of oxyl, 8.0 g of triphenylphosphine, and 18.9 g of propylene glycol monomethyl ether acetate were stirred at 80 ° C until the acid value became 2 mgKOH / g or less. Subsequently, 161.6 g of propylene glycol monomethyl ether acetate was added to and dissolved in 520.5 g of the obtained reaction product, and then 24.2 g of 1,2,3,6-tetrahydrophthalic anhydride was added at 90 ° C. By reacting for 4 hours, alkali-soluble resin-III was obtained. The obtained alkali-soluble resin-III had an acid value of 23 mgKOH / g, a polystyrene equivalent weight average molecular weight Mw measured by GPC of 3000, and a double bond equivalent of 120 g / mol.

<Dispersant-I>
"BYK-LPN21116" manufactured by Big Chemie (acrylic AB composed of an A block having a quaternary ammonium base and a tertiary amino group in a side chain and a B block having no quaternary ammonium base and a tertiary amino group Block copolymer, amine value is 70 mgKOH / g, acid value is 1 mgKOH / g or less.)
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). The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in all the repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.

<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxybutanol

<Photopolymerization initiator-I>
OXE-01 (oxime ester photoinitiator) manufactured by BASF

<Photopolymerizable monomer>
DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.
<Additive-I>
KAYAMER PM-21 (phosphate containing methacryloyl group) manufactured by Nippon Kayaku Co., Ltd.
<Additive-II>
SH6040 (3-glycidoxypropyltrimethoxysilane) manufactured by Toray Dow Corning
<Surfactant>
DIC Mega Fuck F-554

<Preparation of pigment dispersions 1-6>
The pigment, dispersant, alkali-soluble resin, and solvent described in Table 1 were mixed so that the mass ratio described in Table 1 was achieved. The amounts of the dispersant and the alkali-soluble resin in Table 1 are solid amounts, and the amount of the solvent includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.
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 6.

<Preparation of photosensitive coloring compositions 1-13>
[Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples 1 to 6]
Using the pigment dispersions 1 to 4 and 6 prepared above, each component is added so that the ratio in the total solid content of the photosensitive coloring composition is the mixing ratio of Tables 2 to 4, and further, the total solid content The solvent was added so that a content rate might be 22 mass%, and PGMEA / MB = 80/20 (mass ratio), and it stirred and dissolved, and prepared the photosensitive coloring compositions 1-13. Evaluation was performed by the method described later using each of the obtained photosensitive coloring compositions.

<Creation of evaluation board>
Each photosensitive coloring composition was apply | coated using the spinner so that the film thickness after a heat baking might be set to 2.5 micrometers on a glass substrate ("AN100" by AGC company). Then, it was heated and dried on a hot plate at 90 ° C. for 90 seconds to form a coating film.
The obtained coating film was subjected to an overall exposure process without using a mask. Intensity at a wavelength of 365nm is used ultraviolet is 32 mW / cm ^2, the exposure amount was 70 mJ / cm ^2. Moreover, ultraviolet irradiation was performed under air.

Subsequently, a developer composed of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used, and the water pressure was 0 at 25 ° C. After performing the shower development at 15 MPa, the development was stopped with pure water and washed with a water spray. The shower development time was developed for 50 seconds.
The substrate was cured by heating and baking in an oven at 230 ° C. for 20 minutes to obtain a substrate for evaluation having a colored layer.

<Creation of blue substrate>
Using the pigment dispersion 5 prepared above, each component is added so that the ratio in the total solid content of the photosensitive coloring composition is as follows, and the content ratio of the total solid content is 22% by mass. PGMEA was added as described above, and the mixture was stirred and dissolved to prepare a photosensitive coloring composition 14.

Pigment dispersion 5 41.67% by mass
Alkali-soluble resin-I 34.98 mass%
Photopolymerizable monomer 19.25% by mass
Photoinitiator-I 4.00 mass%
Surfactant 0.10% by mass

  Next, the same operation as in <Creation of Evaluation Substrate> was performed except that the film thickness after heating and baking was adjusted to 1.0 μm to obtain a blue substrate having a blue layer.

<Evaluation of optical density (OD)>
The optical density (OD) of each of the colored layer of the obtained substrate for evaluation and the blue layer of the blue substrate was measured with a transmission densitometer (“D200-II” manufactured by Gretag Macbeth). From these measured values, the optical density in a state where the colored layer and the blue layer were laminated was calculated. Next, the optical density (OD / μm) per unit film thickness of only the colored layer of the evaluation substrate was calculated. The results are shown in Tables 2 to 4, respectively.

<Evaluation of transmittance, absorbance, and color tone at a wavelength of 400 to 500 nm>
Spectrophotometer UV-manufactured by Shimadzu Corporation with the light transmittance and absorbance of the wavelength 380 to 780 nm of the obtained substrate for evaluation and the blue substrate every 1 nm and a glass substrate not coated with the photosensitive coloring composition as a control. Measurement was performed using 3150.

And the average transmittance | permeability is calculated by averaging the measured value of the transmittance | permeability every 1 nm in the wavelength of 400-500 nm of each board | substrate, Then, in the state which accumulated the board | substrate for evaluation and the blue board | substrate using those calculated values The average transmittance was calculated and evaluated according to the following criteria. In the case of a blue substrate alone, the average transmittance at a wavelength of 400 to 500 nm is increased. Therefore, it is preferable that the value of the average transmittance is decreased by further laminating a colored layer.
In the same procedure, the transmittance at a wavelength of 400 nm, the transmittance at a wavelength of 450 nm, and the transmittance at a wavelength of 500 nm were calculated, and the results are shown in Tables 2 to 4.

(Wavelength 400-500 nm average transmittance)
○: 5% or less ×: Over 5%

  Next, the average absorbance was calculated by averaging the measured values of absorbance every 1 nm in the wavelength of 400 to 500 nm of each evaluation substrate. Similarly, the average absorbance at a wavelength of 500 to 700 nm was calculated, and the ratio of the average absorbance at a wavelength of 400 to 500 nm to the average absorbance at a wavelength of 500 to 700 nm was calculated. The results are shown in Tables 2-4.

Next, the chromaticity coordinates (x, y) in the xy chromaticity diagram in the XYZ color system in a state where the evaluation substrate and the blue substrate are overlapped are set every 1 nm of wavelengths 380 to 780 nm of each evaluation substrate and blue substrate. Color tone evaluation was performed by calculating from the transmittance and the profile (emission spectrum) of the light source in FIG.
As a result of the color tone, Example 1 (x, y) = (0.255, 0.608), Example 2 (x, y) = (0.327, 0.631), Example 3 (x, y) ) = (0.263, 0.437), Reference Example 1 (x, y) = (0.258, 0.581), Reference Example 2 (x, y) = (0.231, 0.614), Reference Example 3 (x, y) = (0.244, 0.617), Reference Example 4 (x, y) = (0.338, 0.594), Reference Example 5 (x, y) = (0. 319, 0.613) and Reference Example 6 (x, y) = (0.301, 0.633), all of which proved to be practically sufficient.

<Making a substrate for mechanical property evaluation>
Each photosensitive coloring composition of Examples 1-3 and the comparative example 1 was apply | coated using the spinner on the glass substrate (Asahi Glass Co., Ltd. "AN100"). After vacuum drying, a coating film was formed by heating and drying on a hot plate at 90 ° C. for 90 seconds.
The obtained coating film was subjected to exposure treatment using an exposure mask having a complete transmission opening of a circular pattern with various diameters of 5 to 50 μm in diameter (5 to 20 μm: every 1 μm, 25 μm to 50 μm: every 5 μm). . The exposure gap (distance between the mask and the coated surface) was 250 μm. The irradiation light intensity at a wavelength 365nm is used ultraviolet is 32 mW / cm ^2, the exposure amount was 70 mJ / cm ^2. Moreover, ultraviolet irradiation was performed under air.

Subsequently, a developer composed of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used, and the water pressure was 0 at 25 ° C. After 0.05 MPa shower development, development was stopped with pure water and washed with water spray. The shower development time was adjusted between 10 and 120 seconds, and was 1.3 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 20 minutes to cure the pattern to obtain a substantially cylindrical spacer pattern having a height of 2.5 μm.

<Evaluation of mechanical properties>
Among the obtained spacer patterns, the elastic restoration rate was measured according to the following procedure for a pattern having a bottom diameter of 27 ± 2 μm.
As a micro-hardness meter for load-unloading test, a Fischer Instruments H100C product is used, a flat indenter with a measurement temperature of 23 ° C. and a diameter of 50 μm is used, and a load is applied to the spacer at a constant speed (5 mN / sec). In addition, when the load reached 150 mN, the load was held for 5 seconds, followed by unloading at the same speed, and when the load dropped to 0 mN, the load was held for 5 seconds to obtain a load-displacement curve. From this load-displacement curve, the largest displacement value was calculated as the maximum displacement H [max], and the displacement after the load became 0 mN and held for 5 seconds was calculated as the final displacement H [Last].
Next, the elastic recovery rate was calculated by the following formula, and the elastic recovery rate was evaluated as follows. Each result was shown to Tables 2-4.

Elastic recovery rate (%) = {(maximum displacement H [max] −final displacement H [Last])
/ Maximum displacement H [max]} × 100

(Elastic recovery rate)
○: 90% or more ×: less than 90%

In Table 2, from the comparison between Examples 1 and 2 and Comparative Example 1, the content ratio of the colorant in the total solid content of the photosensitive coloring composition is 23% by mass or less, so that the mechanical properties of the colored spacer are reduced. It turns out that becomes favorable. The plastic deformation when a load is applied to the colored spacer by making the content ratio of the colorant in the total solid content 23% by mass or less, that is, by preventing the content ratio of the colorant not elastically deforming from becoming excessively high. It is considered that the elastic recovery rate is improved.
In Table 2 and 3, the photosensitive coloring composition whose content rate of the yellow pigment in all the coloring agents is 40 mass% or more from the comparison with Examples 1, 3 and Reference Example 1 and Comparative Examples 2 and 3. It can be seen that the average transmittance at a wavelength of 400 to 500 nm is sufficiently low by using. It is because the light of wavelength 400-500 nm which is permeate | transmitted without being absorbed in a blue layer is fully light-shielded by containing the yellow pigment more than the said lower limit.
Furthermore, from the comparison between Example 1 and Comparative Example 4, when a photosensitive coloring composition containing not only a yellow pigment but also a red pigment was used, the optical density (OD) in a state where the blue substrate was overlaid. It can be seen that the light shielding property is practically sufficient.

From the comparison of Example 1 in Table 2 and Reference Examples 2 and 3 in Table 4, the average transmittance of 400 to 500 nm is sufficiently low regardless of the type of red pigment, and the optical density (OD) in the state where the blue substrate is overlaid. ) Is also high enough.
Further, from comparison between Example 1 in Table 2 and Reference Examples 4 to 6 in Table 4, even when an orange pigment is used instead of a red pigment, the average transmittance at a wavelength of 400 to 500 nm is sufficiently low, and a blue substrate It can be seen that the optical density (OD) in the state of overlapping is sufficiently high.

Claims (9)

A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound,
The content ratio of the colorant (a) is 23% by mass or less in the total solid content of the photosensitive coloring composition,
(A) the colorant comprises a yellow pigment, a red pigment and / or an orange pigment;
(A) The photosensitive coloring composition characterized by the content rate of the said yellow pigment in a coloring agent being 40 mass% or more.   The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, and C.I. I. The photosensitive coloring composition according to claim 1, comprising at least one selected from the group consisting of CI Pigment Yellow 150.   The red pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 254, and C.I. I. The photosensitive coloring composition of Claim 1 or 2 containing at least 1 sort (s) chosen from the group which consists of pigment red 272.   The orange pigment is C.I. I. Pigment orange 13, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. The photosensitive coloring composition of any one of Claims 1-3 containing at least 1 sort (s) chosen from the group which consists of pigment orange 72.   The photosensitive coloring composition of any one of Claims 1-4 whose content rate of the said (a) coloring agent is 1 mass% or more in the total solid of a photosensitive coloring composition.   The photosensitive coloring composition of any one of Claims 1-5 which is an object for colored spacer formation.   Hardened | cured material obtained by hardening | curing the photosensitive coloring composition of any one of Claims 1-6.   The coloring spacer comprised from the hardened | cured material of Claim 7.   An image display device comprising the colored spacer according to claim 8.

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