TW201905592A - Photosensitive coloring composition, cured product, colored spacer, and image display device - Google Patents

Abstract

Provided are a photosensitive colored composition capable of forming a colored spacer having low light leakage at a wavelength of 400 nm to 500 nm and superior mechanical properties, the colored spacer, and an image display device provided with the colored spacer. One of embodiments of the photosensitive colored composition of the present invention comprises (a) a coloring agent, (b) an alkali soluble resin, (c) a photopolymerization initiator, and (d) an ethylenic unsaturated compound, wherein the content of (a) the coloring agent with respect to total solid content of the photosensitive colored composition is equal to or less than 23 wt%, (a) the coloring agent contains an orange pigment, and the content of the orange pigment with respect to (a) the coloring agent is equal to or more than 45 wt%.

Description

Photosensitive coloring composition, cured material, colored spacer, and image display device

The present invention relates to a photosensitive coloring composition and the like. Specifically, the present invention relates to a photosensitive coloring composition which can be preferably used for forming a colored spacer in a color filter such as a liquid crystal display, and the like obtained by curing the photosensitive coloring composition. A cured product and a colored spacer, and an image display device including the colored spacer. Part of the contents disclosed in the description of the Japanese Patent Application No. 2017-129366 filed with the Japan Patent Office on June 30, 2017, the scope of the patent application, the drawings and the abstract, and the documents cited in this specification It is hereby incorporated by reference in its entirety.

Liquid crystal displays (LCDs) use the property of switching the arrangement of liquid crystal molecules by the on / off of a voltage applied to the liquid crystal. On the other hand, many members constituting a unit of a liquid crystal display are formed by a method using a photosensitive composition typified by a photolithography method. For reasons such as easy formation of fine structures and easier handling of large-area substrates, it is expected that the photosensitive composition will be applied to a wide range in the future. In addition, the backlight device used in the liquid crystal display is characterized by higher resolution, lower cost, thinner appearance, and the like. Now LED (Light Emitting Diode) backlight devices are being used in the mobile terminal or television industry. used widely.

Recently, in order to cope with further high-definition and high-brightness of color liquid crystal displays, in active matrix liquid crystal displays, an integrated color having a color filter placed on the substrate side of a TFT (Thin Film Transistor) element has been proposed. The filter method (COA method) or the integrated black matrix method (BOA method) in which a black matrix is provided only on the TFT element substrate side. According to this method, as compared with the case where a black matrix is formed on the color filter side, it is not necessary to retain the position alignment range with the active element side, so that the aperture ratio can be increased. As a result, higher brightness can be achieved. For the structure of such a black matrix, a high light-shielding property is required or light leakage in a visible light region is suppressed as much as possible.

In addition, along with the simplification of the structure and manufacturing steps of the liquid crystal display, a so-called integration of a columnar spacer, a photosensitive spacer, and a black matrix, which is useful for maintaining a constant interval between two substrates in the liquid crystal display, has also been developed. Spacer. As such a colored spacer, a colored spacer using a plurality of organic colored pigments as a pigment has been proposed (for example, refer to Patent Documents 1 and 2). On the other hand, as in Patent Documents 3 to 5, a liquid crystal display having a color filter layer with one or two or more layers provided on the facing portion of the colored spacer in the frame portion is also proposed. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Korean Published Patent No. 10-2011-0027079 [Patent Document 2] International Publication No. 2013/115268 [Patent Document 3] Korean Published Patent No. 10-2013-0015734 [Patent Document 4] Korea Patent Publication No. 10-2014-0119912 [Patent Document 5] Korean Publication No. 10-2017-0017447

[Problems to be solved by the invention]

The inventors of the present invention and others have found that in various panel structures, particularly in a liquid crystal display having an LED backlight device, a structure in which a blue color filter layer is provided on the facing portion of the colored spacer on the frame portion. In this case, the blue light component from the LED is easily transmitted, and in the colored spacer formed using the photosensitive coloring composition described in Patent Document 1 or 2, a large amount of light leakage at a wavelength of 400 to 500 nm occurs. In addition, when manufacturing a liquid crystal display, since the substrate having the colored spacers is pressed to the opposite substrate, the colored spacers must be deformed by the external pressure in the pressure-bonding step and the external pressure may be removed. It will also return to its original shape when it needs to have mechanical properties such as elastic recovery.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive coloring composition capable of forming a colored spacer with suppressed light leakage at a wavelength of 400 to 500 nm and excellent mechanical properties. [Technical means to solve the problem]

The present inventors made diligent research in order to solve the above-mentioned problems, and as a result, found that by using a specific pigment 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 Can solve the above-mentioned problems, thereby completing the present invention. That is, the present invention has the following configurations [1] to [11].

[1] A photosensitive coloring composition characterized by comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, In the total solid content of the photosensitive coloring composition, the content ratio of the (a) colorant is 23% by mass or less, the (a) colorant contains an orange pigment, and the orange color in the (a) colorant is The content ratio of the pigment is 45% by mass or more. [2] The photosensitive coloring composition according to [1], wherein the orange pigment contains at least one selected from the group consisting of CI Pigment Orange 13, CI Pigment Orange 43, CI Pigment Orange 64, and CI Pigment Orange 72. 1 species. [3] The photosensitive coloring composition according to [1] or [2], wherein the content ratio of the blue pigment and the purple pigment in the (a) colorant is 50% by mass or less.

[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the (a) colorant further contains a yellow pigment. [5] The photosensitive coloring composition according to [4], wherein the yellow pigment contains at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, and C.I. Pigment Yellow 150. [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the content ratio of the coloring agent (a) in the total solid content of the photosensitive coloring composition is 1 mass %the above.

[7] The photosensitive coloring composition according to any one of [1] to [6], which is used to form a colored spacer.

[8] A photosensitive coloring composition characterized by comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, The photosensitive coloring composition is used to form a colored spacer. In the total solid content of the photosensitive coloring composition, the content ratio of the (a) colorant is 23% by mass or less, and The chromaticity coordinates (x, y) satisfy 0.40 ≦ x ≦ 0.55 and 0.35 ≦ y ≦ 0.50. [9] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [8]. [10] A colored spacer comprising the hardened material as described in [9]. [11] An image display device including the colored spacer according to [10]. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive coloring composition, a cured product, and a coloring spacer capable of forming a coloring spacer with suppressed light leakage at a wavelength of 400 to 500 nm and excellent mechanical properties, and further includes a drawing having such a coloring spacer. Like display device.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof. In the present invention, the term "(meth) acrylic acid" means "acrylic and / or methacrylic acid", and the same applies to "(meth) acrylate" and "(meth) acrylfluorenyl".

The so-called "(co) polymer" means including both homopolymer and copolymer, and the so-called "acid (anhydride)" and "(anhydrous) ... acid" means including both the acid and its anhydride . In the present invention, the "acrylic resin" means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylate having a carboxyl group.

In the present invention, the term "monomer" refers to a term referring to a so-called high molecular substance (polymer), and its meaning includes dimer, trimer, and Polymer and so on. 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 below. In the present invention, the "weight average molecular weight" means a weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography). In the present invention, unless otherwise specified, the "amine value" means an amine value in terms of effective solid content, which is expressed by the mass of alkali and equivalent KOH per 1 g of the solid content of the dispersant. Value. The measurement method is described below. On the other hand, unless otherwise specified, the "acid value" indicates an acid value in terms of effective solid content, and is calculated by neutralization titration.

In addition, in this specification, the percentage or part represented by "mass" has the same meaning as the percentage or part represented by "weight". In the present specification, specific examples of pigments may be represented by pigment numbers, and terms such as "C.I. Pigment Red 2" mean color index (C.I.).

[Photosensitive coloring composition] 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 as essential components. As needed, it may further contain adhesion improving agents such as silane coupling agents, surfactants (coatability improving agents), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, development improvers, ultraviolet absorbers, anti- The other formulation ingredients such as an oxidizing agent are usually used in a state of being dissolved or dispersed in a solvent.

In the photosensitive coloring composition of the first aspect of the present invention, in the total solid content of the photosensitive coloring composition, the content ratio of the (a) colorant is 23% by mass or less, and the (a) colorant contains An orange pigment, and the content ratio of the orange pigment in the (a) colorant is 45% by mass or more.

On the other hand, the photosensitive coloring composition of the second aspect of the present invention is a photosensitive coloring composition for forming a colored spacer, and in the total solid content of the photosensitive coloring composition, the above (a) colorant is The content ratio is 23% by mass or less, and the chromaticity coordinates (x, y) in the xy chromaticity diagram satisfy 0.40 ≦ x ≦ 0.55 and 0.35 ≦ y ≦ 0.50.

Hereinafter, unless otherwise specified, the "photosensitive coloring composition of the present invention" refers to both the above-mentioned photosensitive coloring composition and the second aspect of the photosensitive coloring composition.

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

In the photosensitive coloring composition of the present invention in a first aspect, (a) the colorant contains an orange pigment, and (a) the content ratio of the orange pigment in the (a) colorant is 45% by mass or more. Since the orange pigment has a maximum wavelength of absorption peak in the absorption spectrum in the vicinity of a wavelength of 440 to 490 nm, it is considered that by containing an orange pigment, light leakage at a wavelength of 400 to 500 nm can be effectively reduced, especially by using an orange pigment The content ratio is set to the above lower limit value or more, and this light leakage can be reduced to a practically sufficient level. In addition, the orange pigment has a wide absorption band at a wavelength of 500 to 600 nm, and is also effective in terms of easily increasing the optical density (OD). On the other hand, since it has less absorption up to the wavelength of 400 nm, it has less overlap with the absorption band of the photopolymerization initiator, and is also effective from the viewpoint of photohardenability and sensitivity.

Examples of orange pigments include CI 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. Among them, in terms of dispersibility or light-shielding properties, it is preferable to use CI pigment oranges 13, 43, 64, and 72. When the photosensitive coloring composition is hardened by ultraviolet rays, it is preferable to use ultraviolet absorption rates. The lower one is an orange pigment, and from this viewpoint, the CI pigment orange 64 and 72 are more preferably used, and the CI pigment orange 64 is more preferable.

As long as the content ratio of the orange pigment in the (a) colorant is 45% by mass or more, it is not particularly limited. From the viewpoint of significantly suppressing the transmittance at a wavelength of 400 to 500 nm, it is preferably 50% by mass or more, more It is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass. On the other hand, from the viewpoint of using the optical characteristics of a coloring agent other than an orange pigment to widen the absorption band, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass. % Or less, particularly preferably 80% by mass or less. The combination of the upper limit and the lower limit is, for example, preferably 45 to 95% by mass, more preferably 50 to 90% by mass, still more preferably 60 to 85% by mass, and even more preferably 70 to 80% by mass.

(a) The coloring agent may contain a coloring agent other than an orange pigment (hereinafter referred to as "other coloring agent"). Examples of the other coloring agents include pigments and dyes. From the viewpoint of heat resistance, pigments are preferred, and from the viewpoint of hue, photocurability, and sensitivity, organic pigments are preferred.

Examples of the pigment include organic coloring pigments such as a yellow pigment, a red pigment, a blue pigment, a purple pigment, a green pigment, and a brown pigment. Examples of the yellow pigment include: CI 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, 173, 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 viewpoints of dispersibility and reliability, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is preferable, and CI Pigment Yellow 138, 139, From the viewpoint of light-shielding properties, 150 is particularly preferably CI Pigment Yellow 139.

Examples of the red pigment include CI 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, 179, 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 them, in terms of light-shielding property and dispersibility, preferably, CI Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 Further preferred examples include CI Pigment Red 177, 209, 224, and 254. In terms of dispersibility or light-shielding properties, it is preferable to use CI Pigment Red 177, 254, and 272. When the photosensitive coloring composition is hardened by ultraviolet rays, it is preferable to use ultraviolet absorption ratios. The lower one is a red pigment, and from this viewpoint, CI pigment reds 254 and 272 are more preferably used.

Examples of the blue pigment include CI 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 them, from the viewpoint of light-shielding properties, preferably, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60 are mentioned, and further preferably: CI Pigment Blue 15: 6,16. In terms of dispersibility or light-shielding properties, it is preferable to use CI Pigment Blue 15: 6, 16, 60, and when the photosensitive coloring composition is hardened by ultraviolet rays, it is preferable to use ultraviolet absorption. From the standpoint of the lower rate, the blue pigment is more preferably CI Pigment Blue 60. On the other hand, as described in Korean Registered Patent No. 10-1840984, it is preferable to use C.I. Pigment Blue 16 from the viewpoints of reliability, light-shielding properties, and elastic recovery.

Examples of the purple pigment include CI 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. Pigment Violet 19 and 23 are preferred, and C.I. Pigment Violet 23 is more preferred. On the other hand, from the viewpoint of dispersibility, C.I. Pigment Violet 29 is preferably used.

Examples of the green pigment include CI 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. Pigment Green 7, 36 is preferred.

Examples of brown pigments include C.I. Pigment Brown 23, 25, 26, 28, 38, 41, 83, and 93. Among them, C.I. Pigment Brown 26, 28, 83, and 93 are preferably mentioned from the viewpoint of considering both near-infrared transmittance and light-shielding properties.

Among these organic coloring pigments, a yellow pigment or a red pigment is preferable, and a yellow pigment is more preferable because it has an absorption band near a wavelength of 400 to 500 nm. When a yellow pigment is contained, the content ratio of the yellow 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 further preferably 10% by mass or more. It is particularly preferably 20% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and even more preferably 30% by mass or less. When it is set to the above lower limit value, the transmittance at a wavelength of 400 to 500 nm tends to be low, and when it is set to the above upper limit value, the optical density (OD) tends to be high. The combination of the upper limit and the lower limit is, for example, preferably 1 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 10 to 40% by mass, even more preferably 20 to 35% by mass, and even more preferably 20 -30% by mass.

When a red pigment is contained, the content ratio of the red pigment in the (a) colorant is not particularly limited, but it is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. It is particularly preferably 10% by mass or more, more preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and even more preferably 15% by mass or less. When it is at least the above lower limit value, the optical density (OD) tends to be high, and when it is at most the above upper limit value, the transmittance at a wavelength of 400 to 500 nm tends to be low. The combination of the upper limit and the lower limit is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 20% by mass, still more preferably 5 to 15% by mass, and even more preferably 10 to 15% by mass.

From the viewpoint of color tone, it is preferable that the content ratio of organic coloring pigments other than yellow pigments and red pigments, such as blue pigments and purple pigments, be low. From this viewpoint, the total content ratio of the blue pigment and the purple pigment in the (a) colorant is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less, particularly It is preferably 20% by mass or less, and most preferably 0% by mass. That is, it is preferable that the (a) colorant does not contain a blue pigment and a purple 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, still more preferably 30% by mass or less, even more preferably 20% by mass or less, and most preferably 0 quality%. By setting it to be below the above-mentioned upper limit value, there is a tendency to have a good hue.

(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, still more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass %. By setting it to be below the above-mentioned upper limit value, there is a tendency to have a good hue.

On the other hand, from the viewpoint of light-shielding properties, a blue pigment and / or a purple pigment may be contained. In this case, the total content ratio of the blue pigment and the purple pigment in the (a) colorant is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more, and particularly preferably It is preferably 10% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, even more preferably 15% by mass or less. When it is more than the said lower limit value, there exists a tendency for optical density (OD) to become high, and when it is less than the said upper limit value, there exists a tendency for the transmittance | permeability of a wavelength of 400-500 nm to fall. The combination of the upper limit and the lower limit is, for example, preferably 2 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 8 to 30% by mass, even more preferably 10 to 20% by mass, and even more preferably 10 -15% by mass.

As another colorant, a black pigment may be contained. Examples of the black pigment include organic black pigments and inorganic black pigments. Examples of the organic black pigment include a group 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. At least 1 kind of organic black pigment.

[Chemical 1]

In formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , fluorine atom, or chlorine atom; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is 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 selected from the group consisting of R ² and R ^3, R ³ and R ⁴ At least one combination of R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may be directly bonded to each other, or an oxygen atom, a sulfur atom, NH Or NR ¹¹ bridged and bonded to each other; 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, and 3 to 12 carbon atoms A cycloalkenyl group or an alkynyl group having 2 to 12 carbon atoms.

The geometric isomer of the compound represented by the general formula (1) has the following nuclear structure (where the substituents in the structural formula are omitted), and it is likely that the most stable is the trans-trans isomer.

[Chemical 2]

In the case where the compound represented by the general formula (1) is anionic, it is preferred to use any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, Transition metal, primary ammonium, secondary ammonium, trialkylammonium and other tertiary ammonium, tetraalkylammonium and other quaternary ammonium or organometallic complexes to compensate their charges. When the geometric isomer of the compound represented by the general formula (1) is anionic, the same salt is preferred.

Among the substituents of the general formula (1) and the definitions of these, the masking rate tends to be high, so the following are preferred. The reason is that the following substituents are considered non-absorptive and do not 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, and further preferably a hydrogen atom. R ³ and R ⁸ are each independently, preferably 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 group, SO ₃ H or SO ₃ ^-, further 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 .

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

Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl , Norbornyl, base, norcaryl, fluorenyl, fluorenyl, norpinyl, fluorenyl, 1-adamantyl, or 2-adamantyl.

Alkenyl groups having 2 to 12 carbon atoms are, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butane Alken-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-fluorenyl-1-buten-3-yl, 2-methyl-3-butene-2- Radical, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexene-1- Base, 2,4-cyclohexadiene-1-yl, 1-p-pinene-8-yl, 4 (10) -pawnene-10-yl, 2-noren-1-yl, 2,5 -Nordien-1-yl, 7,7-dimethyl-2,4-norbornadien-3-yl or camphenyl.

Examples of alkynyl groups having 2 to 12 carbon atoms are 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, and 2-methyl-3-butyn-2- , 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyne-6-yl, cis-3-methyl-2-pentene-4-yne -1-yl, trans-3-methyl-2-pentene-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyne -9-yl, 1-decyne-10-yl or 1-dodecyne-12-yl.

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).

[Chemical 3]

As a specific example of such an organic black pigment, the trade name is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF). The organic black pigment is preferably used by being dispersed by a dispersant, a solvent, and a method described below. In addition, if a sulfonic acid derivative of the compound represented by the general formula (1) or a sulfonic acid derivative of the compound, particularly a sulfonic acid derivative of the compound represented by the general formula (2), or the above is present during dispersion. The sulfonic acid derivative of the geometrical isomer of the compound may improve dispersibility or preservation. As the organic black pigment, in terms of optical characteristics and reliability, it is preferable to use the organic black pigment described in Korean Laid-Open Patent No. 10-2018-0052502 or Korean Laid-Open Patent No. 10-2018-0052864. The organic black pigment described in the publication.

Examples of other organic black pigments include aniline black, cyanine black, and black. Carbon black, which is an inorganic black pigment, can also be used. Examples of the carbon black include the following carbon blacks.

Manufactured 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 Degussa company: Printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G , Printex P, Printex U, Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 Cabot Corporation: Monarch (registered trademark, Same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0 , REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8 Made by Birla: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750

Carbon black can also be used as a resin coating. If carbon black coated with a resin is used, it has the effect of improving the adhesion to the glass substrate or the volume resistance value. As the carbon black coated with a resin, for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used. In terms of volume resistance or dielectric constant, resin-coated carbon black can be suitably used.

These pigments are preferably used in such a manner that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard of the average particle diameter is the number of pigment particles. In addition, in the photosensitive coloring composition, the average particle diameter of a pigment is a value calculated | required from the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). The particle size measurement is performed on a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if a concentration recommended by a measuring device is available, the concentration is determined according to this concentration) at 25 ° C. Perform the measurement.

Moreover, as another coloring agent, in addition to the said pigment, a dye can also be used. Examples of dyes that can be used as other colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methylene chloride. Basic dyes and so on. Examples of the azo dye include: CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, and the like.

Examples of the anthraquinone dye include CI reduction blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI disperse red 60, CI disperse blue 56, CI disperse blue 60 and so on. In addition, examples of the phthalocyanine dyes include Cipad Blue 5 and the like, and examples of quinone imine dyes include CI Basic Blue 3 and CI Basic Blue 9. Examples of the quinoline dyes include CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64, and the like. Examples of the nitro dye include CI acid yellow 1, CI acid orange 3, CI disperse yellow 42 and the like.

On the other hand, in the photosensitive coloring composition of the present invention in the second aspect, as long as (a) the colorant can be made into the chromaticity coordinates (x, y) of the xy chromaticity diagram described below, 0.40 is satisfied. The coloring agent or a combination of coloring agents of the photosensitive coloring composition of ≦ x ≦ 0.55 and 0.35 ≦ y ≦ 0.50 is not particularly limited.

For example, a red pigment and a yellow pigment are used as the (a) colorant, and the content ratio is adjusted so that the chromaticity coordinates (x, y) satisfy the above range. Also include: a combination of red, yellow, and purple pigments; a combination of brown and yellow pigments; a combination of brown, yellow, and purple pigments; a combination of orange and yellow pigments; a combination of orange and red pigments Combination; combination of orange pigment, yellow pigment and red pigment; combination of orange pigment and purple pigment; combination of orange pigment and blue pigment; combination of orange pigment, blue pigment and purple pigment. Also, those listed in the first aspect may be applied.

Table 1 shows specific examples of pigment types whose chromaticity coordinates (x, y) satisfy the above range and their content ratios, and the values of the chromaticity coordinates (x, y) in each specific example. In addition, the content ratio of the pigment in a table | surface is a value in the total solid content of a photosensitive coloring composition.

[Table 1]

The abbreviations in Table 1 are as follows. Y139: C.I. Pigment Yellow 139 R254: C.I. Pigment Red 254 Br41: C.I. Pigment Brown 41

<(B) Alkali-soluble resin> The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth) acrylate resins and acrylic acid. Based resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolac resins, polyvinyl phenol resins, and the like, among them, from the viewpoint of excellent plate-making properties, they can be suitably used ( b1) epoxy (meth) acrylate resin (b2) acrylic resin. These may be used singly or in combination of plural kinds.

<(B1) Epoxy (meth) acrylate resin> (b1) Epoxy (meth) acrylate resin is based on epoxy resin (epoxy compound), α, β-unsaturated monocarboxylic acid, and / Or a resin obtained by reacting a hydroxyl group formed by a reaction of an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with a polybasic acid and / or an anhydride thereof. Before reacting the polybasic acid and / or its anhydride with a hydroxyl group, it is reacted with a compound having two or more substituents capable of reacting with the hydroxyl group, and then reacted with the polybasic acid and / or its anhydride. The obtained resin is also included in the (b1) epoxy (meth) acrylate resin.

The resin obtained by reacting the carboxyl group of the resin obtained in the above reaction with a compound having a reactive functional group is also included in the (b1) epoxy (meth) acrylate resin. As described above, the epoxy (meth) acrylate resin does not substantially have an epoxy group in the chemical structure, and is not limited to "(meth) acrylate". Since the epoxy compound (epoxy resin) is Raw materials, and "(meth) acrylate" is a representative example, so it is named as usual.

As the (b1) epoxy (meth) acrylate-based resin used in the present invention, specifically, from the viewpoint of developability and reliability, the following epoxy (meth) acrylate-based resins can be suitably used. Resin (b1-1) and / or epoxy (meth) acrylate resin (b1-2) (hereinafter sometimes referred to as "carboxyl-containing epoxy (meth) acrylate resin").

<Epoxy (meth) acrylate resin (b1-1)> 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 an alkali-soluble resin obtained by further reacting with a polybasic acid and / or its anhydride. <Epoxy (meth) acrylate resin alkali-soluble resin (b1-2)> By adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monomer having a carboxyl group to an epoxy resin A carboxylic acid ester, an alkali-soluble resin obtained by further reacting with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.

Here, the epoxy resin system also includes a raw material compound before the resin is formed by thermosetting. As the epoxy resin, it can be appropriately selected from known epoxy resins and used. As the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. The phenolic compound is preferably a compound having a phenolic hydroxyl group of two or more valences, and may be a monomer or a polymer. As the kind of epoxy resin used as a raw material, a cresol novolac epoxy resin, a phenol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, and triphenol methane can be suitably used. Type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, epoxy resin as reaction product of addition polymerization reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin , An adamantyl group-containing epoxy resin, a fluorene type epoxy resin, and the like, such a main chain having an aromatic ring can be suitably used.

As specific examples of the epoxy resin, for example, bisphenol A epoxy resin (for example, "jER (registered trademark, the same below) -828", "jER-1001", "manufactured by Mitsubishi Chemical Corporation"), jER-1002 "," jER-1004 "," NER-1302 "(epoxy equivalent 323, softening point 76 ° C, etc.) manufactured by Nippon Kayaku Co., Ltd., bisphenol F-type resin (such as" jER manufactured by Mitsubishi Chemical Corporation " -807 "," jER-4004P "," jER-4005P "," jER-4007P "," NER-7406 "(epoxy equivalent 350, softening point 66 ° C, etc.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S Type epoxy resin, biphenyl glycidyl ether (such as "jER-YX4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (such as "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "JER-152", "jER-154", "DEN-438" manufactured by Dow Chemical Co., Ltd., (ortho, meta, p) cresol novolac type epoxy resin (e.g. "EOCN ( Registered trademark, the same below) -102S "," EOCN-1020 "," EOCN-104S "), triglycidyl isocyanurate (such as Nissan "TEPIC (registered trademark)" manufactured by Chemical Co., Ltd., triphenol methane epoxy resin (such as "EPPN (registered trademark, the same below) -501", "EPPN-502", "EPPN- 503 "), alicyclic epoxy resin (" Celloxide (registered trademark, the same below) 2021P "," Celloxide EHPE "manufactured by Daicel), and a phenol resin obtained by the reaction of dicyclopentadiene and phenol A glycidyl epoxy resin (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), represented by the following general formulae (B1) to (B4) Epoxy, etc. Specifically, as the epoxy resin represented by the following general formula (B1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and as the epoxy resin represented by the following general formula (B2), As the "NC-3000" manufactured by Nippon Kayaku Co., Ltd., as the epoxy resin represented by the following general formula (B4), "ESF-300" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. can be cited.

[Chemical 4]

In the above general formula (B1), a is an average value and represents a number from 0 to 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, and benzene. , Naphthyl, or biphenyl. In addition, a plurality of R ¹¹¹ present in one molecule may be the same or different.

[Chemical 5]

In the above general formula (B2), b is an average value and represents a number from 0 to 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, and benzene. , Naphthyl, or biphenyl. In addition, a plurality of R ¹²¹ existing in one molecule may be the same or different.

[Chemical 6]

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

[Chemical 7]

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

[Chemical 8]

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

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

Examples of the α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxyl group include (meth) acrylic acid, butenoic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, Monocarboxylic acids such as p-vinyl benzoic acid, α-haloalkyl, (meth) acrylic acid, alkoxy, halogen, nitro, and cyano substituents; 2- (meth) acrylic acid ethoxyethyl succinate 2- (meth) acryloxyethyl adipate, 2- (meth) acryloxyethyl phthalate, 2- (meth) acryloxy hexahydrophthalate Ethyl ester, 2- (meth) acryloxyethyl maleate, 2- (meth) acryloxypropyl succinate, 2- (meth) acryloxy adipic acid Propyl ester, 2- (meth) acryloxypropyl phthalate, 2- (meth) acryloxypropyl phthalate, 2- (methyl) maleic acid Acrylic acid oxypropyl ester, 2- (meth) acrylic acid oxybutyl succinate, 2- (meth) acrylic acid oxybutyl adipate, 2- (methyl) hydrogen phthalate Acrylic ethoxybutyl ester, 2- (meth) acrylic ethoxybutyl phthalate, maleic acid 2- (meth) acrylic ethoxylate Esters (meth); monomers made by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid; or (meth) acrylic acid Addition of hydroxyalkyl ester, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate to succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride) (Anhydride) monomers; (meth) acrylic acid dimers, etc. Among these, in terms of sensitivity, (meth) acrylic acid is particularly preferred.

As a method for adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid having a carboxyl group and an epoxy resin can be formed at a temperature of 50 to 150 ° C in the presence of an esterification catalyst. Perform the reaction. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; tetramethylammonium chloride and tetraethyl chloride Quaternary ammonium salts such as ammonium and dodecyltrimethylammonium chloride.

Furthermore, 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 be used alone or in combination of two or more. And use. The amount of the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. A more preferable range is 0.7 to 1.1 equivalents. When the amount of the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group is set to the above-mentioned lower limit value or more, there is a problem that the amount of the unsaturated group introduced can be suppressed. It is easy to make the subsequent reaction with polybasic acid and / or its anhydride sufficient. On the other hand, by making it below the above-mentioned upper limit value, it can be seen that it is easy to suppress the remaining of unreacted products of α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid having a carboxyl group, and it is easy to The tendency to make the hardening properties good.

Examples of the polybasic acid and / or its anhydride include those selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and pyromellitic acid. , Trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, internal methylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, biphenyltetra One or two or more of carboxylic acids and their anhydrides.

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

Regarding the addition reaction of a polybasic acid and / or its anhydride, a known method can also be used. It can be used to add α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated carboxyl group to epoxy resin. The reaction of the monocarboxylic acid ester is continued under the same conditions to obtain the target substance. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and more preferably It is in a range of 20 to 140 mgKOH / g. When it is more than the said lower limit value, there exists a tendency for alkaline developability to become favorable, and when it is below the said upper limit value, there exists a tendency for hardening performance to become favorable.

In addition, during the addition reaction of the polybasic acid and / or its anhydride, polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol can be added to prepare a multi-branched structure.

The carboxyl group-containing epoxy (meth) acrylate resin is generally a reaction product between an epoxy resin and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid having a carboxyl group. After the polybasic acid and / or its anhydride are mixed in the mixture, or the polybasic acid and / or its reactant are mixed with an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, And / or its anhydride and polyhydric alcohol are obtained by heating. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyol is not particularly limited. By heating, polyacids and / or their anhydrides are present in mixtures of epoxy resins with reactants of α, β-unsaturated monocarboxylic acids or α, β-unsaturated monocarboxylic acids with carboxyl groups, and polyols. Any of the hydroxyl groups undergo an addition reaction.

As the carboxyl group-containing epoxy (meth) acrylate resin, in addition to the above, Korean Published Patent No. 10-2013-0022955, Korean Registered Patent No. 10-0965189, and Japanese Patent Special Japanese Patent Application Publication No. 2005-165294 and Japanese Patent Application Publication No. 2006-312704.

The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is generally 1,000 or more, preferably 1500 or more, and more preferably 2000 or more, more preferably 2500 or more, and usually 10,000 or less, preferably 8000 or less, more preferably 6,000 or less, even more preferably 5,000 or less, particularly preferably 4,000 or less. By setting it to be above the lower limit value, there is a tendency that the solubility in the developer can be suppressed from becoming too high, and by setting it to be less than the above upper limit value, the solubility in the developer solution tends to be good. . The combination of the upper limit and the lower limit is, for example, preferably 1,000 to 10,000, more preferably 1500 to 8000, still more preferably 2000 to 6000, still more preferably 2500 to 5000, and even more preferably 2500 to 4000.

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, and further preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and particularly preferably 50 mgKOH / g or less. By setting it to be above the lower limit value, there is a tendency that moderate development solubility can be obtained, and by setting it to be less than the above upper limit value, there is a tendency that the development of the film may be suppressed due to excessive development. The combination of the upper limit and the lower limit is, for example, preferably 10 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g, still more preferably 10 to 100 mgKOH / g, and even more preferably 20 to 50 mgKOH / g.

The chemical structure of the epoxy (meth) acrylate resin (b1) is not particularly limited, and examples thereof include epoxy (meth) acrylates having a partial structure (1) represented by the following general formula (I) Resin (b1-A) (hereinafter sometimes referred to simply as "epoxy (meth) acrylate resin (b1-A)"). The epoxy (meth) acrylate resin (b1-A) has three or more (meth) acrylic fluorenyloxy groups in a partial structure represented by the formula (I), so the ethylene-based bis There are many bonds, and if a colored spacer is formed by using the photosensitive coloring composition containing the resin, the tendency is to increase the crosslinking density, to suppress the elution of impurities into the solvent, and to ensure high reliability. The cross-linking density becomes higher, thereby improving mechanical properties.

(Partial structure (1))

[Chemical 9]

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 represent an alkylene group which may have a substituent, R ⁴ represents an n + 1-valent linking group, and R ⁷ represents an alkylene group which may have a substituent, an alkenyl group which may have a substituent, or an aromatic ring group which may have a substituent; l and m each independently represent an integer of 0 to 12, and n represents an integer of 3 or more, ﹡ Means bond key.

(R ² , R ³ , R ^5, and R ⁶ ) In the formula (I), R ² , R ³ , R ^5, and R ⁶ each independently represent an alkylene group which may have a substituent. The alkylene may be linear, branched, or cyclic, or a combination of these. The number of carbon atoms is not particularly limited, but it is usually 1 or more, and usually 8 or less, preferably 6 or less, more preferably 4 or less, and even more preferably 2 or less. By making it below the said upper limit, there exists a tendency for compatibility with other components to become favorable.

Specific examples of the alkylene group include methylene, ethylene, propyl, butyl, and cyclohexyl. From the viewpoint of compatibility with other components, methylene or Ethylene, more preferably methylene.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. From the viewpoint of ease of synthesis, it is preferably Without replacement.

(R ⁴ ) In the general formula (I), R ⁴ represents an n + 1-valent linking group. The chemical structure of the n + 1 monovalent linking group is not particularly limited, and examples include a n + 1 monovalent hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. From the viewpoint of developability, an aliphatic hydrocarbon group is preferred. The carbon-carbon single bond in the hydrocarbon group may be interrupted by 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.

[Chemical 10]

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

The alkylene group in R ⁷ may be linear, branched, or cyclic, or a combination of these. The carbon number is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less, and more preferably 4 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexyl group, and a cyclohexyl group. From the viewpoint of hardenability, a methylene group or an ethylene group is preferred, and more Ethyl is preferred.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Was replaced.

The alkylene group in R ⁷ may be linear, branched, or cyclic, or a combination of these. The carbon number is not particularly limited, but it is usually 2 or more, preferably 4 or more, and usually 8 or less, and preferably 6 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the alkenyl group include a vinylidene group, an alkenyl group, a butylene group, and a cyclohexene group. From the viewpoint of hardenability, the vinylidene group or the cyclohexene group is preferred. , More preferably vinyl.

Examples of the substituent which the alkenyl group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Was replaced.

Examples of the divalent aromatic ring group in R ⁷ include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. Its carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, even more preferably 15 or less, and particularly preferably It is 10 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, a fluorene ring, a benzofluorene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups. The heteroaromatic ring in the divalent aromatic heterocyclic group may be a monocyclic 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, Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzene Acyl isoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, data ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, The pyridine ring, benzimidazole ring, pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and other groups. Among the divalent aromatic ring groups, from the viewpoint of photohardenability, a benzene ring or a naphthalene ring having two free atomic valences is preferred, and a benzene ring having two free atomic valences is more preferred.

Examples of the substituent which the divalent aromatic ring group may have include an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Among these, from the viewpoint of hardenability, it is preferably unsubstituted.

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

(l and m) In the general formula (I), l and m each independently represent an integer of 0 to 12. From the viewpoint of development adhesion, it is preferably 0 or more, more preferably 1 or more, and from the viewpoint of hardenability, it is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. Particularly preferred is 2 or less. On the other hand, from the viewpoint of hardenability, it is preferably 0.

(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 more preferably 10 or less, more preferably 8 or less, still more preferably 7 or less, and even more preferably 6 or less. When it is more than the said lower limit value, hardenability tends to become favorable, and when it is below the said upper limit value, the developing solubility tends to become favorable. The combination of the upper limit and the lower limit is, for example, preferably from 4 to 10, more preferably from 4 to 8, even more preferably from 4 to 7, and even more preferably from 4 to 6.

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

[Chemical 11]

In the formula (II), R ⁸ represents an alkylene group which may have a substituent, an alkenyl group which may have a substituent, or an aromatic cyclic group which may have a substituent, and ﹡ represents a bonding bond.

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

The alkylene group in R ⁸ may be linear, branched, or cyclic, or a combination of these. The carbon number is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 8 or less, and preferably 6 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexyl group, and a cyclohexyl group. From the viewpoint of hardenability, a methylene group or an ethylene group is preferred, and more Ethyl is preferred.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Was replaced.

The alkylene group in R ⁸ may be linear, branched, or cyclic, or a combination of these. The carbon number is not particularly limited, but it is usually 2 or more, preferably 4 or more, and usually 8 or less, and preferably 6 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the alkenyl group include a vinylidene group, an alkenyl group, a butylene group, and a cyclohexene group. From the viewpoint of hardenability, the vinylidene group or the cyclohexene group is preferred. And more preferably cyclohexenyl.

Examples of the substituent which the alkenyl group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Was replaced.

Examples of the divalent aromatic ring group in R ⁸ include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. Its carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, even more preferably 15 or less, and particularly preferably It is 10 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a thick tetraphenyl ring, a fluorene ring, a benzofluorene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups. The heteroaromatic ring in the divalent aromatic heterocyclic group may be a monocyclic 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, Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzene Acyl isoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, data ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, The pyridine ring, benzimidazole ring, pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and other groups. Among these, from the viewpoint of photohardenability, a benzene ring or a naphthalene ring having two free atomic valences is preferred, and a benzene ring having two free atomic valences is more preferred.

Examples of the substituent which the divalent aromatic ring group may have include an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Among these, from the viewpoint of hardenability, it is preferably unsubstituted.

Among these, from the viewpoint of hardenability, R ^{8 is} preferably an alkenyl group which may have a substituent, more preferably an unsubstituted alkenyl group, and even more preferably a cyclohexenyl group.

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

[Chemical 12]

(Partial structure (3)) Further, the epoxy (meth) acrylate resin (b1-A) preferably has a partial structure (3) represented by the following general formula (III) from the viewpoint of curability. ).

[Chemical 13]

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

(R ⁹ ) In the 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 meaning of the epoxy resin is the same as described above.

(p) In the formula (III), p represents an integer of 1 or more. From the viewpoint of considering both the hardenability and the developing solubility, p is preferably 2. On the other hand, from the viewpoint of hardenability, p is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and from the viewpoint of development solubility, 20 or less is more preferable. It is preferably 15 or less, and further preferably 12 or less. When it is more than the said lower limit value, hardenability tends to become favorable, and when it is less than the said upper limit value, development solubility tends to become favorable.

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

[Chemical 14]

In the formula (III-1), γ represents a divalent linking group, and ﹡ represents a bonding bond. The benzene ring in the formula (III-1) may be further substituted with an arbitrary substituent.

(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, and -CO- or -SO ₂ -from the viewpoint of developing solubility. The alkylene may be linear, branched, or cyclic, or a combination of these. The carbon number is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 8 or less, and preferably 6 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the alkylene group include methylene, ethylene, propyl, butylene, hexyl, cyclohexyl, heptyl, octyl, and dodecyl. From the standpoint of sexuality, methylene or propylene is preferred, and propylene is more preferred.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Was replaced. When there are substituents, the number is not limited, and may be one or two or more.

When two hydrogen atoms of the methylene group (-CH _2- ) in the alkylene group are substituted with a substituent, the two substituents may be bonded to each other to form a hydrocarbon ring. Specific examples of γ in this case include a base represented by the following formula (IV) and a base represented by the following formula (V). ﹡ In the chemical formula represents a bond.

[Chemical 15]

Moreover, as an arbitrary substituent which a benzene ring in the said Formula (III-1) may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, etc. are mentioned, for example. The number of substituents is also not particularly limited, and may be one or two or more. When the benzene ring in the formula (III-1) has a substituent, two benzene rings in the formula (III-1) may be connected via the substituent.

Among these, from the viewpoint of hardenability, γ is preferably an alkylene group which may have a substituent, more preferably an unsubstituted alkylene group, and still 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) represented by the following general formula (III-2) from the viewpoint of hardenability. -2).

[Chemical 16]

In the formula (III-2), ﹡ represents a bonding bond. The benzene ring in the formula (III-2) may be further substituted with an arbitrary substituent.

As an arbitrary substituent which a 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 also not particularly limited, and may be one or two or more. Among these, an alkyl group is preferable, a cycloalkyl group is more preferable, and an adamantyl group is more preferable from a viewpoint of developing adhesiveness.

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

[Chemical 17]

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

(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, and a group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, a linear one is preferable from a viewpoint of development solubility, and a cyclic one is preferable from a viewpoint of development adhesiveness. Its carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethyl group, a n-propyl group, a n-butyl group, a n-hexyl group, a n-heptyl group, and the like. Among these, methylene is preferred from the viewpoint of hardenability. Specific examples of the divalent branched aliphatic group include the above-mentioned divalent linear aliphatic group having methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Structures of butyl, second butyl, third butyl, etc. as side chains. The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, and preferably 5 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoane ring, and an adamantane ring. A radical formed by removing two hydrogen atoms from a ring. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the adamantane ring is preferred.

Examples of the substituent which 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, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

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, and more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, a fluorene ring, a benzofluorene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups. The heteroaromatic ring in the divalent aromatic heterocyclic group may be a monocyclic 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, Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzene Acyl isoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, data ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, Pyridine ring, pyridine ring, quinazoline ring, quinazolinone ring, fluorene ring and other groups. Among these, from the viewpoint of photohardenability, a benzene ring or a naphthalene ring having two free atomic valences is preferred, and a benzene ring having two free atomic valences is more preferred.

Examples of the substituent which 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, a propoxy group, and the like. Among these, from the viewpoint of hardenability, it is preferably unsubstituted.

In addition, examples of the group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups include one or more divalent aliphatic groups described above and one The above-mentioned divalent aromatic ring group is a group formed by linking. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is more than the said lower limit value, hardenability tends to become favorable, and when it is less than the said upper limit value, hardenability tends to become favorable. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is more than the said lower limit value, hardenability tends to become favorable, and when it is less than the said upper limit value, hardenability tends to become favorable.

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

[Chemical 18]

As described above, the benzene ring in the formula (III-3) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy 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 also not particularly limited, and may be one or two or more. Among these, from the viewpoint of hardenability, it is preferably unsubstituted.

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

[Chemical 19]

In the formula (III-4), γ represents a divalent linking group, and ﹡ represents a bonding bond. The benzene ring in the formula (III-4) may be further substituted with an arbitrary substituent.

As γ in the formula (III-4), those described as γ in the formula (III-1) can be preferably used. Moreover, as an arbitrary substituent which a benzene ring in the said Formula (III-4) may have, it is preferable to use what is described as the arbitrary substituent which a benzene ring in said Formula (III-1) may have.

The epoxy (meth) acrylate resin (b1-A) has a partial structure (3-1) in the partial structures (3-1) to (3-4) from the viewpoint of developing solubility. )By.

As a specific manufacturing method of the epoxy (meth) acrylate resin (b1-A), a method described in Japanese Patent Laid-Open No. 2007-119718 can be adopted.

The epoxy (meth) acrylate resin is preferably an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (i) from the viewpoint of curability ( b1-B) (hereinafter may be abbreviated as "epoxy (meth) acrylate resin (b1-B)") or epoxy (methyl) having a partial structure represented by the following general formula (ii) Acrylic resin (b1-C) (Hereinafter, it may be abbreviated as "epoxy (meth) acrylate resin (b1-C)."). From the viewpoint of reliability, an epoxy (meth) acrylate resin (b1-C) is more preferable.

[Chemical 20]

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

[Chemical 21]

In formula (ii), R ^c each 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, and ﹡ represents a bonding 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, and a group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, a linear one is preferable from a viewpoint of development solubility, and a cyclic one is preferable from a viewpoint of development adhesiveness. Its carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethyl group, a n-propyl group, a n-butyl group, a n-hexyl group, a n-heptyl group, and the like. Among these, methylene is preferred from the viewpoint of hardenability. Specific examples of the divalent branched aliphatic group include the above-mentioned divalent linear aliphatic group having methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Structures of butyl, second butyl, third butyl, etc. as side chains. The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, and preferably 5 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoane ring, and an adamantane ring. A radical formed by removing two hydrogen atoms from a ring. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the adamantane ring is preferred.

Examples of the substituent which 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, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

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, and more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, a fluorene ring, a benzofluorene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups. The heteroaromatic ring in the divalent aromatic heterocyclic group may be a monocyclic 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, Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzene Acyl isoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, data ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, Pyridine ring, pyridine ring, quinazoline ring, quinazolinone ring, fluorene ring and other groups. Among these, from the viewpoint of photohardenability, a benzene ring or a naphthalene ring having two free atomic valences is preferred, and a benzene ring having two free atomic valences is more preferred.

Examples of the substituent which 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, a propoxy group, and the like. Among these, from the viewpoint of hardenability, it is preferably unsubstituted.

In addition, examples of the group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups include one or more divalent aliphatic groups described above and one The above-mentioned divalent aromatic ring group is a group formed by linking. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is more than the said lower limit value, hardenability tends to become favorable, and when it is less than the said upper limit value, hardenability tends to become favorable.

Specific examples of the group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups include a group represented by the following formulae (i-A) to (i-E). Among these, from the viewpoint of development solubility, a base represented by the following formula (i-A) is preferred. ﹡ In the chemical formula represents a bond.

[Chemical 22]

As described above, the benzene ring in the formula (i) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy 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 also not particularly limited, and may be one or two or more. Among these, from the viewpoint of hardenability, it is preferably unsubstituted.

The partial structure represented by the general formula (i) is preferably a partial structure represented by the following general formula (i-1) from the viewpoint of hardenability.

[Chemical 23]

In the formula (i-1), R ^a and R ^b have the same meanings as in the above formula (i), R ^X represents a hydrogen atom or a polyacid residue, and ﹡ represents a bonding bond. The benzene ring in the 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 an anhydride thereof. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid , Benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid Or two or more. Among these, from the viewpoint of patterning characteristics, as the polybasic acid, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid are preferred. Dicarboxylic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, and 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 may be mixed ^X is a hydrogen atom and R ^X is a polyacid residue.

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 it is preferably 1 or more, and more preferably 3 or more, and preferably 20 or less, and further preferably 15 or less. When it is more than the said lower limit value, hardenability tends to become favorable, and when it is below the said upper limit value, the developing solubility tends to become favorable.

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

[Chemical 24]

[Chemical 25]

[Chemical 26]

[Chemical 27]

(R ^d ) In the above 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 cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic cyclic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and more preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, particularly preferably 15 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. 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 norane ring, an isoane ring, and an adamantane ring. . Among these, from the viewpoint of reliability, an adamantane ring is preferred.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, more preferably It is 4 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. 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, still more preferably 10 or more, even more preferably 12 or more, and still more preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, a fluorene ring, a benzofluorene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring, etc. Among these, from the viewpoint of patterning characteristics, a ring is preferred.

The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent aliphatic groups. A group in which one or more divalent aromatic ring groups are linked.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, a linear one is preferable from a compatibility viewpoint, and a cyclic one is preferable from a reliability viewpoint. Its carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and more preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethyl group, a n-propyl group, a n-butyl group, a n-hexyl group, a n-heptyl group, and the like. Among these, methylene is preferred from the viewpoint of hardenability. As specific examples of the divalent branched aliphatic group, the divalent linear aliphatic group described above has methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, second butyl, third butyl, and the like have a side chain structure. The number of rings of the divalent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and further preferably 3 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoane ring, and an adamantane ring. A radical formed by removing two hydrogen atoms from a ring. Among these, from the viewpoint of reliability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferred.

Examples of the substituent which 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, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. Its carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and further preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, a fluorene ring, a benzofluorene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups. The heteroaromatic ring in the aromatic heterocyclic group may be a monocyclic 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, Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzene Acyl isoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, data ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, Pyridine ring, pyridine ring, quinazoline ring, quinazolinone ring, fluorene ring and other groups. Among the divalent aromatic ring groups, from the viewpoint of patterning characteristics, a benzene ring having two free atomic valences, a naphthalene ring having two free atomic valences, or a fluorene ring having two free atomic valences is preferred. , More preferably a fluorene ring with 2 free atomic valences.

Examples of the substituent which 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, a propoxy group, and the like. Among these, from the viewpoint of developing solubility and moisture absorption resistance, it is preferably unsubstituted.

In addition, examples of the group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups include one or more divalent aliphatic groups described above and one The above-mentioned divalent aromatic ring group is a group formed by linking. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

Specific examples of the group in which one or more divalent aliphatic groups are connected to one or more divalent aromatic ring groups include the groups represented by the formulae (i-A) to (i-E). Among these, from the viewpoint of reliability, the base represented by the formula (i-C) is preferable.

The cyclic hydrocarbon as the side chain is not particularly limited based on the bonding state of the divalent hydrocarbon group, and examples include a state in which the side chain is substituted for one hydrogen atom of an aliphatic group or an aromatic ring group. Or a cyclic hydrocarbon group as a side chain including one carbon atom of an aliphatic group.

The partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of compatibility.

[Chemical 28]

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

(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 cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic cyclic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and more preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, particularly preferably 15 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. 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 norane ring, an isoane ring, and an adamantane ring. . Among these, from the viewpoint of compatibility, an adamantane ring is preferred.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, still more preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. 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, from the viewpoint of reliability, the ring is preferred.

Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, a third butyl group, a pentyl group, an isopentyl group, and the like. Alkyl groups having 1 to 5 carbons; alkoxy groups having 1 to 5 carbons such as methoxy and ethoxy; nitro; cyano; carboxyl and the like. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

n represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable.

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

As described above, the benzene ring in the formula (ii-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy 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 also not particularly limited, and may be one or two or more. Among these, from the viewpoint of patterning characteristics, it is preferably unsubstituted.

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

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

The partial structure represented by the general formula (ii) is preferably a partial structure represented by the following general formula (ii-2) from the viewpoint of reliability.

[Chem 34]

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

(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 cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic cyclic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 10 or less, and preferably 5 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. 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 norane ring, an isoane ring, and an adamantane ring. . Among these, from the viewpoint of compatibility, an adamantane ring is preferred.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, and preferably 5 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, still more preferably 40 or less, more preferably 30 or less, and even more preferably It is 20 or less, and particularly preferably 15 or less. When it is more than the said lower limit value, there exists a tendency for development adhesiveness to become favorable, and when it is below the said upper limit value, there exists a tendency for hardenability to become favorable. 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, from the viewpoint of reliability, the ring is preferred.

Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, a third butyl group, a pentyl group, an isopentyl group, and the like. Alkyl groups having 1 to 5 carbons; alkoxy groups having 1 to 5 carbons such as methoxy and ethoxy; nitro; cyano; carboxyl and the like. Among these, from the viewpoint of simplicity of synthesis, it is preferably unsubstituted.

Among these, from the viewpoint of compatibility, R ^{β is} preferably a divalent aliphatic ring group, and more preferably a divalent adamantyl ring group. On the other hand, from the viewpoint of reliability, R ^{β is} preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

As described above, the benzene ring in the formula (ii-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxy 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 also not particularly limited, and may be one or two or more. In addition, two benzene rings in formula (ii-2) may be linked via these substituents. Among these, from the viewpoint of patterning characteristics, it is preferably unsubstituted.

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

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

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

[Chemical 39]

In the formula (ii-3), R ^c and R ^d have the same meanings as in the above formula (ii), and R ^Z represents a hydrogen atom or a polyacid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. Furthermore, one OH group can be removed and shared with R ^{Z in} other molecules represented by formula (ii-3), that is, a plurality of formulas (ii-3) can be linked via R ^Z. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid , Benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid Or two or more. Among these, from the viewpoint of patterning characteristics, as the polybasic acid, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid are preferred. Dicarboxylic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, and 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 may be mixed ^X is a hydrogen atom and R ^Z is a polybasic acid residue.

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 it is preferably 1 or more, and more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When it is more than the said lower limit value, hardenability tends to become favorable, and when it is below the said upper limit value, the developing solubility tends to become favorable.

The epoxy (meth) acrylate resin (b1) may be used alone, or two or more resins may be used in combination. In addition, a part of the epoxy (meth) acrylate resin (b1) described above may be replaced with another binder resin and used. That is, the epoxy (meth) acrylate resin (b1) can be used in combination with another binder resin. In this case, the ratio of the epoxy (meth) acrylate resin (b1) in the (b) alkali-soluble resin is preferably 5 mass% or more, and more preferably 10 mass% or more. The content is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and most preferably 50% by mass or more. The content is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less. The combination of the upper limit and the lower limit is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 60% by mass, and most preferably 50 to 60%. quality%.

The other binder resin that can be used in combination with the epoxy (meth) acrylate resin (b1) is not limited, and may be selected from resins commonly used in photosensitive coloring compositions. For example, the binder resins described in Japanese Patent Laid-Open No. 2007-271727, Japanese Patent Laid-Open No. 2007-316620, and Japanese Patent Laid-Open No. 2007-334290 can be cited. From the viewpoint of reliability and surface smoothness, a (meth) acrylic copolymer resin described in International Publication No. 2017/110893 is preferable. Furthermore, other binder resins can be used alone or in combination of two or more.

Moreover, as (b) an alkali-soluble resin, (b2) an acrylic resin is preferably used from the viewpoint of compatibility with a coloring agent, a dispersant, and the like.

Examples of the acrylic resin include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b2-1)") and other copolymerizable ethylenically unsaturated monomer ( Hereinafter, it is a copolymer of "unsaturated monomer (b2-2)"). Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, butenoic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid and maleic anhydride , Unsaturated dicarboxylic acids such as fumaric acid, methyl maleic acid, methyl maleic anhydride, methyl fumaric acid, or their anhydrides; succinic acid mono [2- (methyl ) Mono [(meth) acryloxyalkane] of divalent or higher polycarboxylic acids such as propylene ethoxyethyl] ester, mono [2- (meth) acryl ethoxyethyl] phthalate Omega] esters; ω-carboxy polycaprolactone mono (meth) acrylates are equivalent to mono (meth) acrylates of polymers having carboxyl and hydroxyl groups at both ends; p-vinylbenzoic acid and the like. These unsaturated monomers (b2-1) may be used alone, or two or more kinds may be used in combination.

Examples of the unsaturated monomer (b2-2) include N-position-substituted maleimidines such as N-phenyl maleimide diimide and N-cyclohexyl maleimide diimide. Imine; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinyl benzyl glycidyl ether, fluorene and other aromatic vinyl compounds;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, ( Benzyl methacrylate, polyethylene glycol (polymerization degree 2-10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2-10) 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, iso (meth) acrylate, ( Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxy (meth) acrylate Phenyl ester, ethylene oxide modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3- [(Meth) acryloxymethyl] oxetane, 3-[(meth) acryloxymethyl] -3-ethyloxetane, and other (meth) acrylates;

Cyclohexyl vinyl ether, isoyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl) -3- Vinyl ethers such as ethyloxetane; polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane is equal to a mono (methyl ) Macromonomers of acrylic fluorenyl and the like. These unsaturated monomers (b2-2) may be used alone, or two or more kinds may be used in combination.

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 to 50% by mass. It is more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b2-1) within such a range, there is a tendency that a photosensitive coloring composition excellent in alkaline 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, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Copolymers disclosed in Japanese Patent Laid-Open No. 2004-101728 and Japanese Patent Laid-Open No. 2018-9132. The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method. For example, it can also be obtained from Japanese Patent Laid-Open No. 2003-222717 and Japanese Patent Laid-Open No. 2006. The method disclosed in -259680, International Publication No. 2007/029871, etc. controls its structure or Mw, Mw / Mn.

<(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, addition agents such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be used. Examples of the photopolymerization initiator include metallocene compounds containing titanocene compounds described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Japanese Patent Laid-Open No. 2000 Hexaarylbiimidazole derivatives described in Japanese Patent Publication No. 56118; halomethylated oxadiazole derivatives, halomethyl trimellitic derivatives described in Japanese Patent Laid-Open No. 10-39503; Free radical active agents such as N-aryl-α-amino acids such as phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α- Amine alkyl phenone derivatives; oxime ester compounds described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, and the like.

Specifically, for example, as the metallocene compound, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) bisphenyltitanium, and bis (cyclopentadienyl) bis ( 2,3,4,5,6-pentafluorophenyl) titanium, bis (cyclopentadienyl) bis (2,3,5,6-tetrafluorophenyl) titanium, bis (cyclopentadienyl) Bis (2,4,6-trifluorophenyl) titanium, bis (cyclopentadienyl) bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2,4- Difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] titanium, and the like.

Examples of the biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 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 fluorenediazole derivatives include 2-trichloromethyl-5- (2'-benzofuranyl) -1,3,4-fluorenediazole and 2-trichloro Methyl-5- [β- (2'-benzofuranyl) vinyl] -1,3,4-fluorenediazole, 2-trichloromethyl-5- [β- (2 '-(6' '-Benzofuryl) vinyl)]-1,3,4-fluorenediazole, 2-trichloromethyl-5-furanyl-1,3,4-fluorenediazole, and the like.

Examples of the halomethyl mesitane derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) mesa, and 2- (4-methoxynaphthalene). Methyl) -4,6-bis (trichloromethyl) tris, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) tris, 2- (4-ethoxy Carbonylcarbonylnaphthyl) -4,6-bis (trichloromethyl) are all equal.

Examples of the α-aminoalkyl phenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-olinylpropane-1-one, and 2-benzyl 2-dimethylamino-1- (4-olinylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-olinylphenyl) butane-1 -Ketone, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 1,4-dione 2-ethylhexyl methylaminobenzoate, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzene Formamyl) coumarin, 4- (diethylamino) chalcone and the like.

As a photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate-making properties. When an alkali-soluble resin containing a phenolic hydroxyl group is used, etc., it becomes sensitive in terms of sensitivity. It is disadvantageous, and therefore, such an oxime ester compound having excellent sensitivity is particularly useful. Since the oxime ester compound has both a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates free radicals, a small amount is high in sensitivity, and it is relatively stable to thermal reactions, and a small amount of high sensitivity can be obtained. Photosensitive coloring composition.

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

[Chemical 40]

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 any substituent including an aromatic ring, and R ^22a represents a substituent that may have Alkylalkyl, or arylamidino which may have a substituent, and n represents an integer of 0 or 1.

The carbon number of the alkyl group in R ^21a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, and preferably 15 Hereinafter, it is more preferably 10 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, cyclopentylethyl, and propyl. Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amine group, a fluorenylamino group, and 4- (2-methoxy-1-methyl) ethoxy-2. -Methylphenyl, N-ethenyl-N-ethenoxyamino, and the like are preferably unsubstituted from the viewpoint of ease of synthesis.

Examples of the aromatic ring group in 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. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more 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, from the viewpoint of developability, a phenyl group or a naphthyl group is preferred, and a benzene group is more preferred. base. Examples of the substituent which the aromatic cyclic group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amine group, amidino group, an alkyl group, an alkoxy group, and a group in which these substituents are connected. From a viewpoint, an alkyl group, an alkoxy group, and the group which connected these are preferable, and an alkoxy group which is connected 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 in which the substituent has an alkoxy group connected.

Further, as R ^21b , a substituted carbazolyl group and a substituted 9-oxysulfur group are preferred. Or diphenyl sulfide group which may be substituted. Among these, from the viewpoint of sensitivity, a carbazolyl group which may be substituted is preferred.

The carbon number of the alkyl group in R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 2 or more, preferably 3 or more, and usually 20 or less. It is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. Specific examples of the alkylfluorenyl group include an ethylfluorenyl group, a propionyl group, and a butanyl group. Examples of the substituent which the alkylfluorenyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amine group, and a fluorenylamino group. From the viewpoint of ease of synthesis, an unsubstituted group is preferred.

In addition, the carbon number of the arylfluorenyl group in R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 7 or more, preferably 8 or more, and usually 20 or less. It is preferably 15 or less, and more preferably 10 or less. Specific examples of the arylfluorenyl group include a benzamyl group, a naphthylmethyl group, and the like. Examples of the substituent which the arylfluorenyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amine group, a fluorenylamino 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 alkylfluorenyl group which may have a substituent, more preferably an unsubstituted alkylfluorenyl group, and even more preferably an ethylfluorenyl group.

In addition, in terms of reducing the contamination of the liquid crystal layer by the colorant, the initiator described in Japanese Patent Laid-Open No. 2016-133574 can be suitably used.

The photopolymerization initiator may be used singly or in combination of two or more kinds. If necessary, for the purpose of improving the sensitivity of sensitivity, a photopolymerization initiator is prepared with a sensitizing dye and a polymerization accelerator corresponding to the wavelength of an image exposure light source. Examples of the sensitizing dye include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756. Pigments; Coumarin pigments with heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335; Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335 3-ketocoumarin compounds described in Japanese Patent Publication No. 6-19240; pyrrole methylene pigment described in Japanese Patent Application Laid-Open No. 6-19240; and Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54- Japanese Patent Publication No. 155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. Japanese Patent Application Publication No. 60-88005, Japanese Patent Application Publication No. 59-56403, Japanese Patent Application Publication No. 2-69, Japanese Patent Application Publication No. 57-168088, Japanese Patent Application Publication No. 5-107761, A pigment having a dialkylaminobenzene skeleton described in Japanese Patent Laid-Open No. 5-210240 and Japanese Patent Laid-Open No. 4-288818.

Among these sensitizing dyes, preferred are sensitizing dyes containing an amine group, and further preferred are compounds having an amine group and a phenyl group in the molecule. Particularly preferred are, for example: 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone Ketones, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone and other benzophenone-based compounds; 2- ( P-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzofluorene Azole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2 -(P-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethyl Aminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylamine) Phenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) Compounds containing p-dialkylaminophenyl, such as pyrimidine, and the like. Among them, 4,4'-dialkylaminobenzophenone is the best. The sensitizing dye may be used alone or in combination of two or more.

As the polymerization accelerator, for example, aromatic amines such as p-dimethylaminoethyl benzoate and 2-dimethylaminoethyl benzoate; aliphatic amines such as n-butylamine and N-methyldiethanolamine; hereinafter The thiol compound and the like. A polymerization accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

<(D) Ethylene unsaturated compound> The photosensitive coloring composition of this invention contains (d) an ethylenically unsaturated compound. By containing (d) an ethylenically unsaturated compound, sensitivity improves. The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, and monoesters of a carboxylic acid and a polyhydric or monohydric alcohol having one ethylenically unsaturated bond, and the like. .

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 it is usually two or more, preferably four or more, more preferably five or more, and more preferably eight or less , More preferably 7 or less. If it is more than the said lower limit value, it will become high sensitivity, and if it is less than the said upper limit value, the solubility in a solvent will improve. The combination of the upper limit and the lower limit is, for example, preferably from 2 to 8, more preferably from 4 to 8, and even more preferably from 5 to 7. Examples of the polyfunctional ethylenic monomer include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; and an aliphatic polyhydroxy compound and an aromatic Polyhydroxy compounds such as polyhydroxy compounds, esters obtained by esterification of unsaturated carboxylic acids and polycarboxylic acids, and the like.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates of aliphatic polyhydroxy compounds such as esters, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, The acrylate of the exemplified compound is changed to the methacrylate of the methacrylate, the same is changed to the iconate of the iconate, the butenoate of the butenoate, or the maleate Esters of maleic acid and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol dimethyl. Acrylic esters and methacrylic esters of aromatic polyhydroxy compounds, such as acrylate and pyrogallol triacrylate.

The ester obtained by the esterification reaction of a polycarboxylic acid and an unsaturated carboxylic acid with a polyhydroxy compound is not necessarily a single substance. If a representative specific example is listed, acrylic acid, phthalic acid, and 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 glycerol Condensate, etc.

In addition, as examples of the polyfunctional ethylenic monomer used in the present invention, it is useful to use a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound and a polyol and a hydroxyl group-containing compound. (Meth) acrylic acid urethanes obtained by reacting (meth) acrylic acid esters; such as epoxy acrylic acid of addition reaction products of polyhydric epoxy compounds and hydroxyl (meth) acrylic acid esters or (meth) acrylic acid Esters; Acrylamides such as ethacrylamide; Allyl esters such as diallyl phthalate; Vinyl compounds such as diethylene phthalate.

Examples of the (meth) acrylic acid urethanes include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (made by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (made by Kyoeisha Chemical Co., Ltd. ), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

Among these, from the viewpoint of hardenability, as the (d) ethylenically unsaturated compound, an alkyl (meth) acrylate is preferably used, and dipentaerythritol hexaacrylate is more preferably used. These can be used alone or in combination of two or more.

<(E) Solvent> The photosensitive coloring composition of this invention may contain (e) a solvent. By containing the (e) solvent, a pigment can be disperse | distributed in a solvent, and application | coating tends to become easy. The photosensitive coloring composition of the present invention generally comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, and various other components used as necessary. Use in a state of being dissolved or dispersed in a solvent. Among solvents, an organic solvent is preferred from the viewpoint of dispersibility or coating properties.

Among organic solvents, from the viewpoint of coating properties, it is preferred to select a boiling point in the range of 100 to 300 ° C, and more preferred to select a boiling point in the range of 120 to 280 ° C. The boiling point herein means the boiling point at a pressure of 1013.25 hPa, and all the boiling points are the same below.

Examples of such an organic solvent 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 third butyl ether, diethyl ether 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 -Glycol monoalkyl ethers such as methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethyl Glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and the like class;

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 ethyl Acid esters, propylene glycol monobutyl ether acetate, butyl methoxy acetate, 3-methoxy butyl acetate, amyl methoxy acetate, diethylene glycol monomethyl ether acetate, diethylene glycol mono Diethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl ether Glycol alkyl ether ether acetates such as butyl-3-methoxyacetate; ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diethyl Glycol diacetates such as acid esters; alkyl acetates such as cyclohexyl acetate; pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl Ethers such as ether and dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone , Ketones such as ethylpentyl ketone, methylbutyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone; ethanol, propanol, butanol, hexanol, cyclohexyl Mono- or polyhydric alcohols such as alcohol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol; n-pentane, Aliphatic hydrocarbons such as n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, methylcyclohexene, Alicyclic hydrocarbons such as cyclohexane;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; pentyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, ethylene glycol Alcohol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octoate, butyl stearate, ethyl benzoate, 3-ethyl Methyloxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methylpropionate Chain or cyclic esters such as butyloxypropionate and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Chlorobutane And halogenated hydrocarbons such as chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile.

Examples of the commercially available organic solvents include: mineral spirits, Varsol # 2, Apco # 18 solvent, Apco thinner, Socal solvents No. 1 and No. 2, Solvesso # 150, Shell TS28 solvent, card Bisanol, ethyl carbitol, butyl carbitol, methyl cyrus ("Syrus" is a registered trademark; the same below), ethyl cyrus, ethyl cyrus acetate, a Kiselosu acetate, diethylene glycol dimethyl ether (both are trade names), and the like. These organic solvents may be used alone or in combination of two or more.

In the case where the colored spacer is formed by a photolithography method, it is preferable to select, as the organic solvent, a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred in terms of a good balance in coatability, surface tension, and the like, and relatively high solubility of constituent components in the composition. The 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 preferred. Among these, propylene glycol monomethyl ether is preferred in terms of the solubility of the constituents in the composition. In addition, glycol monoalkyl ethers have high polarity. If the amount is too large, the pigment tends to aggregate, and the storage stability of the photosensitive coloring composition obtained thereafter tends to decrease, such as storage stability. The ratio of the diol monoalkyl ethers is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass.

In addition, it is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as a “high boiling point solvent”). By using such a high-boiling-point solvent in combination, the photosensitive coloring composition becomes difficult to dry, and has the effect of preventing the uniform dispersion state of the pigment in the composition from being damaged by rapid drying. That is, it has the effect of preventing the generation | occurrence | production of the impurity defect by precipitation and solidification of the toner etc. of a slit nozzle tip, for example. In terms of such a high effect, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred.

When a high boiling point solvent is used in combination, the content ratio of the high boiling point solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 5% to 30% by mass. %. By setting it to the above lower limit value, for example, it is possible to suppress the occurrence of impurity defects caused by the precipitation and curing of colorant and the like at the tip of the slit nozzle, and by setting it to the above upper limit value, the combination can be suppressed. The drying temperature of the product becomes slower, which suppresses the tendency of problems such as poor touch in the reduced pressure drying process or pre-baking pore marks.

In addition, the high-boiling point solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a high-boiling point solvent having a boiling point of 150 ° C or higher may not be additionally contained. . Examples of preferred high-boiling solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and , 3-butanediol diacetate, 1,6-hexanol diacetate, glycerol triacetate, and the like.

<(F) Dispersant> The (f) dispersant may be contained in the photosensitive coloring composition of the present invention for the purpose of finely dispersing the (a) colorant and stabilizing the dispersed state. As the (f) dispersant, a polymer dispersant having a functional group is preferred, and in terms of dispersion stability, a polymer dispersant having a functional group such as the following group is preferred: carboxyl group; phosphate group; sulfonic acid Acid group; or such a salt group; primary, secondary or tertiary amine group; quaternary ammonium salt group; a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine and pyridine. Among them, especially from the viewpoint of dispersing a small amount of a dispersant when dispersing a pigment, a polymer dispersant having a basic functional group such as a primary group, a secondary group, or a tertiary amine group; a quaternary ammonium group is particularly preferable. Base; a radical derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, and pyridine.

Examples of the polymer dispersant include a urethane-based dispersant, an acrylic-based dispersant, a polyethylenimine-based dispersant, a polyallylamine-based dispersant, and a polymer containing an amine group. Monomer and macromonomer dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan fatty acid fatty ester Based dispersants, aliphatic modified polyester based dispersants, and the like.

Specific examples of such a dispersant include the following: EFKA (registered trademark; manufactured by BASF), DISPERBYK (registered trademark; manufactured by BYK-Chemie), Disparlon (registered trademark; manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark; manufactured by Lubrizol), KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (made by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark; manufactured by Ajinomoto), and the like. These polymer dispersants may be used singly or in combination of two or more kinds.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, and preferably 50,000 or less. Among these, from the viewpoint of dispersibility of the pigment, the (f) dispersant is preferably a urethane-based polymer dispersant and / or an acrylic polymer dispersant having a functional group, and particularly preferably Contains acrylic polymer dispersant. In terms of dispersibility and storage properties, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferred.

Examples of the urethane-based and acrylic polymer dispersants include DISPERBYK 160 to 166, 182 series (both urethane-based), DISPERBYK 2000, 2001, BYK-LPN21116, etc. (both acrylic-based) (The above are manufactured by BYK-Chemie). As a urethane-based polymer dispersant, if a preferable chemical structure is specifically exemplified, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule and an average molecular weight of 300 to 10,000, And a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having active hydrogen in the molecule with a tertiary amine group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amine group can be made into a quaternary ammonium salt group.

Examples of the polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1,5- Aromatic diisocyanates such as diisocyanate, ditoluidine diisocyanate; hexamethylene diisocyanate, methyl lyme diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate And other aliphatic diisocyanates; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'-diisocyanatodimethylcyclohexane and other alicyclic diisocyanates; Aliphatic diisocyanates with aromatic rings such as xylylene diisocyanate, α, α, α ', α'-tetramethylxylylene diisocyanate; triamine isocyanate, 1,6,11-ten Monoalkane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptane triisocyanate, tris (isocyanate) Acidic phenyl) methane, tris (isocyanatophenyl) phosphorothioate, and other triisocyanates; and terpolymers, water adducts, And such polyol adducts. As the polyisocyanate, a terpolymer of an organic diisocyanate is preferable, and a terpolymer of a toluene diisocyanate and a terpolymer of an isophorone diisocyanate are most preferable. These can be used alone or in combination of two or more.

Examples of the method for producing an isocyanate trimer include the following: using an appropriate trimerization catalyst such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, or a carboxylate; Polyisocyanates undergo partial trimerization of isocyanate groups. After the trimerization is stopped by adding catalyst poisons, unreacted polyisocyanates are removed by solvent extraction and thin-film distillation to obtain the target isocyanurate-containing compounds. Polyisocyanate.

Examples of compounds 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 diol, and polyolefin diene. Alcohols, etc., and the alkoxylation of a single terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and a mixture of two or more of these. Examples of the polyether glycol include polyether diol, polyetherester diol, and a mixture of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing an alkylene oxide, and examples thereof include polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, and polyoxytetramethylene. Glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more of these.

Examples of the polyetherester diol include a reaction of an ether group-containing diol or a mixture with another diol with a dicarboxylic acid or an anhydride thereof, or a polyesterdiol (polyesterester diol). A glycol) is obtained by reacting with an alkylene oxide, and examples thereof include poly (polyoxytetramethylene) adipate. As the polyether glycol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound thereof is preferably alkoxylated with a single terminal hydroxyl group through an alkyl group having 1 to 25 carbon atoms. A compound formed by radicalization.

Examples of the polyester glycol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid). Etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol Alcohol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl Propyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl- 2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5 -Aliphatic diols such as hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol; bishydroxymethyl ring Alicyclic diols such as hexane; aromatic diols such as benzyl alcohol, dihydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine, etc.) Ethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene adipate / Adipate, etc .; or a polylactone diol or a polylactone monool obtained using the above diols or a monohydric alcohol having 1 to 25 carbons, for example, polycaprolactone Lactone glycol, polymethylvalerolactone and mixtures of two or more of these. As the polyester glycol, a polycaprolactone diol or a polycaprolactone having a carbon number of 1 to 25 is used as a starter.

Examples of the polycarbonate diol include polycarbonate (1,6-hexane diester) and polycarbonate (3-methyl-1,5-pentane diester), and the like, and examples of the polyolefin diol include polybutadiene Ethylene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like. These can 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 6000, and still more preferably 1,000 to 4,000.

The compound having an active hydrogen and a tertiary amine 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 amine group, or a thiol group. Among them, an amine group is preferred, especially a primary Amino hydrogen atoms.

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

Examples of the nitrogen-containing heterocyclic ring when the tertiary amine group has a nitrogen-containing heterocyclic ring structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, and indene. Nitrogen-containing five-membered heterocycles such as azole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, and benzothiadiazole ring; pyridine ring, data ring, pyrimidine ring, tricyclic ring , Quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing six-membered heterocyclic rings. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) Imidazole and so on. In addition, if a compound having a triazole ring and an amino group is specifically exemplified, 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 these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3 -Amino-1,2,4-triazole. These can be used alone or in combination of two or more.

The preferred compounding ratio of the raw materials when manufacturing the urethane-based polymer dispersant is 10 to 200 relative to 100 parts by mass of the polyisocyanate compound, and a compound having one or two hydroxyl groups in the molecule and an average molecular weight of 300 to 10,000. 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of the compound having active hydrogen and a tertiary amine group in the molecule, preferably 0.3 to 24 parts by mass.

The production of the urethane-based polymer dispersant is performed in accordance with a known method for producing a polyurethane resin. As the solvent during production, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone and other ketones can be generally used; ethyl acetate, butyl acetate, and acetate Lu Su and other esters; Benzene, toluene, xylene, hexane and other hydrocarbons; diacetone alcohol, isopropanol, second butanol, third butanol and some alcohols; methylene chloride, chloroform and other chlorides; Ethers such as tetrahydrofuran and diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethylsulfine. These can be used alone or in combination of two or more.

In the above-mentioned production, a urethane reaction catalyst can be generally used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron such as iron pyruvate and ferric chloride Department; tertiary amines such as triethylamine, triethylenediamine, etc. These can be used alone or in combination of two or more.

The introduction amount of the compound having an active hydrogen and a tertiary amine group in the molecule is preferably controlled within a range of 1 to 100 mgKOH / g based on the amine value after the reaction. A more preferable range is 5 to 95 mgKOH / g. The amine value is a value expressed in mg of KOH by titrating a basic amine group by acid neutralization to correspond to the acid value. When it is more than the said lower limit value, there exists a tendency for a dispersibility to become favorable, and when it is below the said upper limit value, there exists a tendency for the fall of the developability to be suppressed easily.

Furthermore, in the case where the isocyanate group remains in the polymer dispersant in the above reaction, if the isocyanate group is further destroyed by an alcohol or an amine compound, the stability of the product over time is improved, which is preferable. The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably in the range of 2,000 to 100,000, and more preferably in the range of 3,000 to 50,000. When it is more than the said lower limit, dispersibility and dispersion stability tend to become favorable, and when it is below the said upper limit, there exists a tendency for the solubility or the fall of a dispersibility to be suppressed easily.

On the other hand, as the acrylic polymer dispersant, it is preferable to use an unsaturated group containing a functional group (the functional group referred to herein is the functional group described as the functional group contained in the polymer dispersant). Random copolymers, graft copolymers and block copolymers of monomers and unsaturated monomers without functional groups. These copolymers can be produced by a known method.

Examples of the unsaturated group-containing monomer having a functional group include the following: (meth) acrylic acid, 2- (meth) acrylic acid ethoxyethyl succinate, and 2- (phthalic acid) Unsaturated monomers having a carboxyl group, such as meth) acryloxyethyl ester, 2- (meth) acryloxyethyl hexahydrophthalate, acrylic acid dimer; dimethylamine (meth) acrylate Unsaturated monomers having tertiary amine groups and quaternary ammonium salt groups such as ethyl ethyl ester, diethylamino ethyl (meth) acrylate, and quaternary compounds thereof. These can 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, third butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic ring Hexyl ester, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Tricyclodecyl acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene; N-cyclohexylcis-butenediamidine, N-substituted maleimide, such as N-phenyl maleimide, N-benzyl maleimide, acrylonitrile, vinyl acetate, and poly (meth) acrylate Macromonomers, polystyrene macromonomers, 2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers, and other macromonomers体 等。 Body and so on. These can be used alone or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer containing an A block having a functional group and a B block having no functional group. In this case, the A block contains a source other than the one derived from the above. In addition to the partial structure of the unsaturated group-containing monomer containing a functional group, it may also include a partial structure derived from the unsaturated group-containing monomer containing no functional group, which may be randomly copolymerized or block copolymerized. Either aspect is contained in the A block. The content ratio of the functional group-free partial structure in the A block is usually 80% by mass or less, preferably 50% by mass or less, and further preferably 30% by mass or less.

The B block contains a partial structure derived from the above-mentioned unsaturated group-containing monomer having no functional group, and may also contain two or more partial structures derived from the monomer in one B block. Either the regular copolymerization or the block copolymerization is contained in the B block. This A-B or B-A-B block copolymer is prepared by the living polymerization method shown below, for example. The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method. The polymerization active species of the anionic living polymerization method is an anion, and is represented by the following scheme, for example.

[Chemical 41]

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.

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

[Chemical 42]

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 integers of 1 or more, Ra is ^a hydrogen atom or a monovalent organic group, and R ^b is Ra is ^a different hydrogen atom or a monovalent organic group.

To synthesize the acrylic polymer dispersant, Japanese Patent Laid-Open No. 9-62002 or P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews can be used. et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Right Hand Koichi, Putian Koichi, Polymer Processing , 36, 366 (1987), Tomura Toshiyuki, Enomoto Masao, Polymer Essays, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Well-known methods described in Aida Takusan, Inoue Shoji, Organic Synthetic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987) and the like.

The acrylic polymer dispersant usable in the present invention may be an AB block copolymer or a BAB block copolymer. The A block / B block constituting the copolymer is preferably 1/99 to 80/20. It is particularly preferably 5/95 to 60/40 (mass ratio). By setting it within this range, there is a tendency that a balance between dispersibility and storage stability can be ensured. In addition, the amount of the quaternary ammonium salt group in 1 g of the AB block copolymer and the BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol. By setting the range to be within this range, good quality can be ensured. Tendency to be decentralized.

In addition, in such a block copolymer, an amine group generated in the manufacturing process may be contained, and its amine value is about 1 to 100 mgKOH / g. From the viewpoint of dispersibility, it is preferably 10 Above mgKOH / g, more preferably above 30 mgKOH / g, still more preferably above 50 mgKOH / g, still more preferably below 90 mgKOH / g, even more preferably below 80 mgKOH / g, even more preferably 75 mgKOH / g or less. The combination of the upper limit and the lower limit is, for example, preferably from 10 to 90 mgKOH / g, more preferably from 30 to 80 mgKOH / g, and even more preferably from 50 to 75 mgKOH / g. Here, the amine value of dispersants such as these block copolymers is represented by the mass of KOH equivalent to the alkali equivalent per 1 g of solid components other than the solvent in the dispersant sample. Determination. Accurately weigh 0.5 to 1.5 g of the dispersant sample into a 100 mL beaker and dissolve it with 50 mL of acetic acid. Using an automatic titration device with a pH electrode, the solution was neutralized and titrated with a 0.1 mol / L HClO ₄ acetic acid solution. Using the inflection point of the titration pH curve as the end point of the titration, the amine value was determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S) [where W is the dispersant sample weighing amount [g], V is the titration end point of the titration [mL], S is the dispersant Sample solid content concentration [mass%]] The acid value of the block copolymer also depends on the presence and type of the acidic group that is the source of the acid value. Generally, a lower value is preferred, usually 10 mgKOH / The weight average molecular weight (Mw) of g or less is preferably in the range of 1,000 to 100,000. By setting it as the said range, there exists a tendency for favorable dispersibility to be ensured.

When the acrylic polymer dispersant has a quaternary ammonium salt group as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferable to have the following A repeating unit represented by formula (i) (hereinafter sometimes referred to as "repeating unit (i)").

[Chemical 43]

In the above formula (i), R ³¹ to R ³³ are each independently a hydrogen atom, 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. Among R ³¹ to R ³³ Two or more 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 number of carbon atoms of the alkyl group which may have a substituent among R ³¹ to R ³³ in the formula (i) is not particularly limited, but it is usually 1 or more, preferably 10 or less, and more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Moreover, it may contain cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent among R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, benzene is preferred Group, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

The number of carbon atoms of the aralkyl group which may have a substituent among R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include phenylmethyl (benzyl), phenylethyl (phenethyl), phenylpropyl, phenylbutyl, and phenylisopropyl. Among these, Is preferably phenylmethyl, phenylethyl, phenylpropyl, or phenylbutyl, and more preferably phenylmethyl or phenylethyl.

Among these, from the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ are each independently an alkyl group or an aralkyl group, and specifically, it is preferable that R ³¹ and R ³³ are each independently a methyl group or an ethyl group. And R ³² is phenylmethyl or phenylethyl, more preferably R ³¹ and R ³³ are methyl, and R ³² is phenylmethyl.

When the acrylic polymer dispersant has a tertiary amine group as a functional group, from the viewpoint of dispersibility, it is preferable to have a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as "Repeat Unit (ii)").

[Chemical 44]

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, 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 ³⁵ and R ³⁶ may be Bonded to each other to form a cyclic structure, R ³⁷ is a hydrogen atom or a methyl group, and Z is a divalent linking group.

In addition, as the alkyl group which may have a substituent among R ³⁵ and R ³⁶ in the formula (ii), those exemplified as R ³¹ to R ³³ in the formula (i) can be preferably used. 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) can be preferably used. In addition, as the aralkyl group which may have a substituent among R ³⁵ and R ³⁶ in the formula (ii), those exemplified as R ³¹ to R ³³ in the formula (i) can be preferably used.

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

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

In the above formula (i) and (ii), examples of the divalent linking group X and Z, for example, include carbon atoms of the alkyl group having 1 to 10 extension, of 6 to 12 carbon atoms, an arylene group, -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 (alkoxyalkyl group) having 2 to 10 carbon atoms], etc., are preferred It is -COO-R ⁴⁴ -group. Further, in the above formula (I), as counter anions Y ^{-, include: Cl -, Br -, I} -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - and the like.

The content ratio of the repeating unit represented by the above formula (i) is not particularly limited, and from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (i) and that represented by the above formula (ii) The total content of the repeating unit is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, even more preferably 35 mol% or less, and more preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and even more preferably 30 mol% or more.

The content ratio of the repeating unit represented by the above formula (i) to the total repeating unit of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferably 1 mol% or more. It is preferably 5 mol% or more, further preferably 10 mol% or more, and more preferably 50 mol% or less, more preferably 30 mol% or less, and still more preferably 20 mol% or less. It is 15 mol% or less.

The content ratio of the repeating unit represented by the above formula (ii) to the total repeating unit of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferably 5 mol% or more, more It is preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and more preferably 60 mol% or less, more preferably 40 mol% or less, and more preferably It is 30 mol% or less, particularly preferably 25 mol% or less.

In addition, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter referred to as "" Repeating unit (iii) ").

[Chemical 45]

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

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

In addition, in the formula (iii), n is preferably 1 or more, more preferably 2 or more, and more preferably 10 or less from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent. It is preferably 5 or less.

The content ratio of the repeating unit represented by the formula (iii) in the total repeating unit of the polymer dispersant is not particularly limited, but it is preferably 1 mole% or more, and more preferably 2 mole% or more. It is more preferably 4 mol% or more, more preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. When it is in the said range, there exists a tendency for compatibility with compatibility with a binder component, such as a solvent, and dispersion stability.

The polymer dispersant preferably has a repeating unit represented by the following formula (iv) from the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability (hereinafter sometimes referred to as "Repeat Unit (iv)").

[Chemical 46]

In the formula (iv), R ³⁸ is 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, and R ³⁹ is a hydrogen atom or a methyl group.

The number of carbons 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, more preferably 4 or more, and more preferably 10 or less. It is more preferably 8 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be either linear or branched. Moreover, it may contain cyclic structures, such as a cyclohexyl group and 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 it is usually 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. . Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Among these, benzene is preferred Group, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

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 it is usually 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 the following. Specific examples of the aralkyl group include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl. Of these, phenylmethyl, Phenylethyl, phenylpropyl, or phenylbutyl, more preferably phenylmethyl or phenylethyl.

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 which the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Examples of the substituent which the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. Moreover, the linear alkyl group represented by R ³⁸ includes any of a linear chain and a branched chain.

In addition, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating unit of the polymer dispersant is preferably 30 mol% or more, and more preferably 40 mol from the viewpoint of dispersibility. % Or more, more preferably 50 mol% or more, more preferably 80 mol% or less, and more preferably 70 mol% or less.

The polymer dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii), and repeating unit (iv). Examples of such repeating units include repeating units derived from the following monomers: styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylic acid salts such as (meth) acrylic acid, chloride, and the like Monomers; (meth) acrylamide-based monomers such as (meth) acrylamide, N-hydroxymethacrylamine; vinyl acetate; acrylonitrile; allyl glycidyl ether, butyric acid glycidyl Ether; monomers such as N-methacryl fluorenylline.

From the viewpoint of further improving dispersibility, the polymer dispersant preferably includes an A block having repeating units (i) and repeating units (ii) and a B having no repeating units (i) and repeating units (ii). Block copolymer The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing not only a quaternary ammonium salt group but also a tertiary amine group into the A block, the dispersing ability of the dispersant tends to be significantly improved. The B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).

The repeating unit (i) and the repeating unit (ii) may be contained in the A block in any form of random copolymerization and block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may each contain two or more types in one A block. In this case, each repeating unit may be in random copolymerization or block copolymerization. It is contained in this A block.

The A block may contain repeating units other than repeating units (i) and (ii). Examples of such repeating units include the (meth) acrylate-based monomers described above. Body repeating unit and so on. The content of repeating units (i) and repeating units other than repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably in the A block. This repeat unit is not included.

The B block may contain repeating units other than repeating units (iii) and (iv). Examples of such repeating units include repeating units derived from the following monomers: styrene, α-methylstyrene, etc. Styrene-based monomers; (meth) acrylic acid-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide-based monomers such as (meth) acrylamide, N-hydroxymethacrylamide Body; vinyl acetate; acrylonitrile; allyl glycidyl ether, butyric acid glycidyl ether; monomers such as N-methacryl phosphonoline. The content of the repeating units (iii) and repeating units other than the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably the B block. This repeating unit is not included.

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

<Other Formulation Ingredients of Photosensitive Coloring Composition> In the photosensitive coloring composition of the present invention, in addition to the above components, adhesion improving agents such as silane coupling agents, surfactants (coating property improving agents), and pigments can be appropriately blended. Derivatives, photoacid generators, crosslinking agents, mercapto compounds, development improvers, ultraviolet absorbers, antioxidants and other additives.

(1) Adhesion improving agent In order to improve adhesion to a substrate, the photosensitive coloring composition of the present invention may contain an adhesion improving agent. As the adhesion improving agent, a silane coupling agent, a phosphate group-containing compound, and the like are preferable. As the type of the silane coupling agent, one of an epoxy-based, (meth) acrylic-based, and amine-based one may be used alone, or two or more of them may be used in combination.

Examples of preferred silane coupling agents include (meth) methyl 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like. Acrylic methoxysilanes; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Ethoxysilanes such as diethoxysilyl, 3-glycidyloxypropyltriethoxysilane; Ureasilane such as 3-ureidopropyltriethoxysilane; 3-isocyanate groups Isocyanate-based silanes such as propyltriethoxysilane, and particularly preferred are silane coupling agents of epoxysilane. The phosphate group-containing compound is preferably a (meth) acrylfluorenyl group-containing phosphate ester, and is preferably represented by the following general formula (g1), (g2), or (g3).

[Chemical 47]

In the general formulae (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 phosphate group-containing compounds may be used singly or in combination of two or more kinds.

(2) Surfactant In order to improve the coating property, a surfactant may be contained in the photosensitive coloring composition of the present invention.

As the surfactant, for example, various anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, non-ionic surfactants are preferred in terms of the low possibility of adversely affecting various characteristics. Among them, fluorine-based or silicon-based surfactants are effective in terms of coating properties. Surfactant. Examples of such a surfactant include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (by BYK-Chemie), and KP340 ( (Made by Shin-Etsu Silicones), MEGAFAC F-470, MEGAFAC F-475, MEGAFAC F-478, MEGAFAC F-554, MEGAFAC F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (Manufactured by Daikin), L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M), and the like. Furthermore, one type of surfactant may be used, or two or more types may be used in any combination and ratio.

(3) Pigment derivative In order to improve dispersibility and storage stability, a pigment derivative may be contained in the photosensitive coloring composition of the present invention as a dispersion aid. Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, difluorene-based, anthraquinone-based, and indigo Derivatives of the Shihlin system, the hydrazone system, the purple ring ketone system, the diketopyrrolopyrrole system, the difluorene system, and the like, among them, phthalocyanine system and quinophthalone system are preferred. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamido group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylamino group, a hydroxyl group, a carboxyl group, and a fluorenyl group. Those bonded to the pigment skeleton directly or via an alkyl group, an aryl group, or a heterocyclic group are preferably a sulfonic acid group. These substituents may substitute a plurality of pigment skeletons.

Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolopyrrole Sulfonic acid derivatives of pyrrole, sulfonic acid derivatives of diamidine, and the like. These can be used alone or in combination of two or more.

(4) Photoacid generator The so-called photoacid generator is a compound capable of generating an acid by ultraviolet rays, and a crosslinking reaction such as a melamine compound is caused by the action of an acid generated during exposure. . Among the photoacid generators, those having a high solubility in a solvent, particularly those having a high solubility in a solvent used in the photosensitive coloring composition are preferred, and examples thereof include diphenylphosphonium, xylylphosphonium, and benzene. (P-anisyl) 錪, bis (m-nitrophenyl) 錪, bis (p-thirdbutylphenyl) 第三, bis (p-chlorophenyl) 錪, bis (n-dodecyl) 錪, p Diaryl fluorene such as isobutylphenyl (p-tolyl) hydrazone, p-isopropylphenyl (p-tolyl) fluorene; or chloride, bromide of triaryl fluorene such as triphenyl fluorene; or fluoroborate , Hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc .; or organoboron such as n-butyl triphenyl borate, diphenyl benzamidine methyl hydrazone, etc. Complexes; or 2-methyl-4,6-bis (trichloromethyl) tri, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) Compounds and the like are not limited thereto.

(5) Cross-linking agent A cross-linking agent can be further added to the photosensitive coloring composition of the present invention. For example, a melamine or guanamine-based compound can be used. Examples of such a crosslinking agent include melamine or guanamine-based compounds represented by the following general formula (6).

[Chemical 48]

In formula (6), R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms. When R ⁶¹ is a -NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ^{67 each} represent a -CH ₂ OR ⁶⁸ group, 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 represents -CH ₂ OR ⁶⁸ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ^66, and R ⁶⁷ each independently represent hydrogen or -CH ₂ OR ⁶⁸ , and R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms . 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 an alkyl group, an alkoxy group, or a halogen atom may be bonded to the phenyl or naphthyl group And other substituents. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1) includes hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, and hexamethoxymethylmelamine , Pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, etc.

[Chemical 49]

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 represents − CH ₂ OR ⁶⁸ group, the remaining of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each independently represent a hydrogen atom or a -CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents a hydrogen atom or an alkane base.

In addition, the guanamine-based compound corresponding to the general formula (6), that is, the compound in which R ⁶¹ in the general formula (6) is an aryl group includes tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanidine. Amine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, and the like.

Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group may 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-tri-2-one (commonly known as N-ethyldimethyloltrione) or its dimethyl ether body, dimethyloltrimethylene urea or its dimethyl ether body , 3,5-bis (hydroxymethyl) perhydro-1,3,5-fluorenedi-4-one (commonly known as dimethylol urea) or its dimethyl ether body, tetramethylol glyoxal Alkyl urea or its tetramethyl ether.

Furthermore, these crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

(6) Mercapto compound As a polymerization accelerator, a mercapto compound may be added in order to improve the adhesion to the substrate.

Examples of the type of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexamethylene dithiol, decanedithiol, and 1,4-dimethylthiobenzene. , Butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate Acid ester, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithio Propionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylol Propane tris (3-mercaptobutyrate), pentaerythritol tetra (3-mercaptobutyrate), pentaerythritol tri (3-mercaptobutyrate), ethylene glycol bis (3-mercapto isobutyrate), succinic acid Alcohol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutoxyethyl) -1,3, 5-tri-2,4,6 (1H, 3H, 5H) -trione and other heterocyclic mercapto compounds or aliphatic polyfunctional mercapto compounds . These may be used singly or in combination of two or more kinds.

<Component blending amount in the photosensitive coloring composition> In the photosensitive coloring composition of the present invention, the content ratio of (a) the colorant in the total solid content of the photosensitive coloring composition is 23% by mass or less. Since (a) the colorant is a component that does not deform elastically, it is considered that the mechanical properties of the obtained colored spacer are improved by setting the content ratio to the above-mentioned upper limit value or less. The total solid content of the photosensitive coloring composition is not particularly limited as long as the content ratio of (a) the colorant is 23% by mass or less, preferably 22% by mass or less, more preferably 20% by mass or less, and further It is preferably 18% by mass or less, more preferably 16% by mass or less, even more preferably 15% by mass or less, most preferably 14% by mass or less, more preferably 1% by mass or more, and more preferably 5% by mass or more. It is more preferably 8% by mass or more, still more preferably 10% by mass or more, and even more preferably 12% by mass or more. By setting the content ratio of (a) the colorant below the above-mentioned upper limit, the mechanical properties tend to be good, sufficient plate-making properties are easily obtained, and electrical reliability is excellent. Above the lower limit, sufficient light-shielding properties tend to be obtained. The combination of the upper limit and the lower limit is, for example, preferably 1 to 22% by mass, more preferably 5 to 20% by mass, still more preferably 8 to 18% by mass, even more preferably 10 to 16% by mass, and even more preferably 10 to 15% by mass, and most preferably 12 to 14% by mass.

The content ratio of the pigment in the photosensitive coloring composition of the present invention is not particularly limited. In the total solid content of the photosensitive coloring composition, it is usually 23% by mass or less, preferably 22% by mass or less, and more preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 16% by mass or less, even more preferably 15% by mass or less, most preferably 14% by mass or less, more preferably 1% by mass or more, more It is preferably at least 5 mass%, more preferably at least 8 mass%, even more preferably at least 10 mass%, and even more preferably at least 12 mass%. When the content ratio of the pigment is set to the above-mentioned upper limit value or less, the mechanical properties become favorable, and sufficient plate-making characteristics are easily obtained, and the electrical reliability is excellent. Further, when the content ratio of the pigment is set to the above-mentioned lower limit value or more, There is a tendency to obtain sufficient light-shielding properties. The combination of the upper limit and the lower limit is, for example, preferably 1 to 22% by mass, more preferably 5 to 20% by mass, still more preferably 8 to 18% by mass, even more preferably 10 to 16% by mass, and even more preferably 10 to 15% by mass, and most preferably 12 to 14% by mass.

The content ratio of the orange pigment in the total solid content of the photosensitive coloring composition of the first aspect is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and even more preferably It is 10% by mass or more, particularly preferably 15% by mass or more, and usually 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, still more preferably 40% by mass or less, particularly It is preferably 30% by mass or less, and most preferably 20% by mass or less. When it is set to the above lower limit value, sufficient light-shielding property can be ensured, and transmittance at a wavelength of 400 to 500 nm can be suppressed. When it is set to the above upper limit value, sufficient plate-making performance tends to be easily obtained. . The combination of the upper limit and the lower limit is, for example, preferably 1 to 60% by mass, more preferably 5 to 50% by mass, still more preferably 5 to 45% by mass, still more preferably 8 to 40% by mass, and even more preferably 10 to 30. Mass%, preferably 15 to 20 mass%.

From the viewpoint of color tone, the photosensitive coloring composition of the first aspect preferably has a low content ratio of blue pigment and purple pigment in all solids, preferably 30% by mass or less, and more preferably 25% by mass. % Or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and most preferably 0% by mass, that is, not contained. On the other hand, from the viewpoint of light-shielding properties, a blue pigment and / or a purple pigment may be contained. In this case, the content ratio of the blue pigment and the purple pigment in the total solid content is preferably 1% by mass. Above, more preferably 5 mass% or more, still more preferably 8 mass% or more, particularly preferably 10 mass% or more, most preferably 15 mass% or more, more preferably 30 mass% or less, and even more preferably 25 mass % Or less, more preferably 20% by mass or less. When it is more than the said lower limit value, sufficient light-shielding property tends to be obtained, and when it is below the said upper limit value, the color tone close to black tends to be obtained. The combination of the upper limit and the lower limit is, for example, preferably 1 to 30% by mass, more preferably 5 to 30% by mass, still more preferably 8 to 25% by mass, even more preferably 10 to 20% by mass, and even more preferably 15 -20% by mass.

From the viewpoint of light-shielding properties, the photosensitive coloring composition of the first aspect preferably has a low content ratio of the yellow pigment in the total solid content, preferably 30% by mass or less, and more preferably 25% by mass or less. It is more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and most preferably 0% by mass, that is, not contained. On the other hand, from the viewpoint of suppressing the transmittance at a wavelength of 400 to 500 nm, a yellow pigment may be contained. In this case, the content ratio of the yellow pigment in all solids is preferably 1% by mass or more. It is preferably 3% by mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, and most preferably 15% by mass or more. The content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. By setting it above the lower limit value, the transmittance at a wavelength of 400 to 500 nm can be suppressed, or a hue close to black can be obtained. By setting it below the above upper limit value, electrical reliability becomes high, and It is possible to increase the optical density (OD). The combination of the upper limit and the lower limit is, for example, preferably 1 to 30% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass, and even more preferably 15 -20% by mass.

In the total solid content of the photosensitive coloring composition of the present invention, the content ratio of (b) alkali-soluble resin is usually 5 mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more, and more It is preferably 30% by mass or more, particularly preferably 35% by mass or more, and usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and more preferably It is preferably 50% by mass or less, and particularly preferably 45% by mass or less. When the content ratio of the (b) alkali-soluble resin is equal to or more than the above-mentioned lower limit value, there is a tendency that the mechanical properties become good and the developability becomes good. Moreover, when it is below the above-mentioned upper limit value, it tends to maintain an appropriate sensitivity, suppress the dissolution of the exposed portion by the developing solution, and suppress a decrease in adhesiveness. The combination of the upper limit and the lower limit is, for example, preferably 5 to 85% by mass, more preferably 10 to 80% by mass, still more preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, and even more preferably 35 to 50% by mass, most preferably 35 to 45% by mass.

(c) The content ratio of the photopolymerization initiator is generally 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more in the total solids of the photosensitive coloring composition of the present invention. It is preferably 2 mass% or more, and usually 15 mass% or less, preferably 10 mass% or less, more preferably 8 mass% or less, still more preferably 7 mass% or less, and even more preferably 5 mass% or less. When the content ratio of the (c) photopolymerization initiator is set to the above-mentioned lower limit value or less, the sensitivity tends to be suppressed. When it is set to the above-mentioned upper limit value or less, the unexposed portion with respect to the developer can be suppressed. This reduces the solubility and suppresses the tendency to develop poorly. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, still more preferably 1 to 8% by mass, even more preferably 2 to 7% by mass, and even more preferably 2 to 5 mass%.

When (c) a photopolymerization initiator is used together with a polymerization accelerator, the content of the polymerization accelerator in all solids of the photosensitive coloring composition of the present invention is preferably 0.05% by mass or more. It is usually 10% by mass or less, preferably 5% by mass or less, and the polymerization accelerator is preferably 0.1 to 50 parts by mass and 0.1 to 20 parts by mass relative to 100 parts by mass of the (c) photopolymerization initiator. Ratio used. When the content ratio of the polymerization accelerator is set to the above lower limit value or more, it is possible to suppress a decrease in sensitivity to exposure light. By setting the content ratio to the above upper limit value or less, it is possible to suppress the unexposed portion from being exposed to the developer. The solubility is reduced, and the tendency of poor development is suppressed. When (c) a photopolymerization initiator is used together with a sensitizing dye, the content ratio of the sensitizing dye in the total solid content of the photosensitive coloring composition is usually from the viewpoint of sensitivity. It is 20% by mass or less, preferably 15% by mass or less, and further preferably 10% by mass or less.

In the total solid content of the photosensitive coloring composition of the present invention, the content ratio of (d) the ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more. It is more preferably 20% by mass or more, particularly preferably 30% by mass or more, and usually 70% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less. When the content ratio of the (d) ethylenically unsaturated compound is equal to or higher than the above-mentioned lower limit value, there is a tendency to maintain an appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress a decrease in adhesiveness. In addition, by setting it to be equal to or less than the above upper limit value, there is a tendency that the permeability of the developer to the exposed portion is suppressed to be high, and a good image tends to be easily obtained. The combination of the upper limit and the lower limit is, for example, preferably 1 to 70% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 60% by mass, even more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass.

On the other hand, the content ratio of (b) the alkali-soluble resin to 100 parts by mass of the (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 further preferably It is 100 parts by mass or more, and 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. By setting it to be above the lower limit value, there is a tendency that it becomes an appropriate developing state without peeling and the like, and by setting it to be below the upper limit value, it is possible to set the dissolution time to be appropriate for the developer. . In addition, as a combination of the upper limit and the lower limit, for example, 50 to 700 parts by mass is more preferable, 80 to 500 parts by mass is more preferable, 80 to 400 parts by mass is more preferable, and 100 to 300 is even more preferable. Parts by mass.

In addition, the photosensitive coloring composition of the present invention uses the (e) solvent, and the content ratio of the total solid content thereof is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass. % Or more, and usually 50 mass% or less, preferably 30 mass% or less, and more preferably 25 mass% or less. The combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass.

When the photosensitive coloring composition of this invention contains (f) dispersing agent, the content rate of (f) dispersing agent in the total solid content of a photosensitive coloring composition is 1 mass% or more normally, Preferably it is 2% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and even more preferably 5% by mass or less. When the content ratio of the (f) dispersant is set to the above lower limit value or more, sufficient dispersibility tends to be easily obtained. When the content ratio of the (f) dispersant is set to the above upper limit value or less, the relative decrease in the ratio of other components can be suppressed. This tends to cause a decrease in sensitivity, plate-making properties, and the like. The combination of the upper limit and the lower limit is, for example, preferably 1 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 1 to 15% by mass, even more preferably 2 to 10% by mass, and even more preferably 2 to 5 mass%.

The content ratio of (f) the dispersant to 100 parts by mass of the (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and usually 50 parts by mass Hereinafter, it is particularly preferably 30 parts by mass or less. When the content ratio of the (f) dispersant is set to the above lower limit value or more, sufficient dispersibility tends to be easily obtained. When the content ratio of the (f) dispersant is set to the above upper limit value or less, the ratio of other components can be suppressed from being reduced. This tends to cause a decrease in sensitivity, plate-making properties, and the like. The combination of the upper limit and the lower limit is, for example, preferably from 5 to 50 parts by mass, more preferably from 10 to 50 parts by mass, and even more preferably from 15 to 30 parts by mass.

When the adhesion improving agent is used, the content ratio is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by weight in the total solids in the photosensitive coloring composition. %. When the content ratio of the adhesion improving agent is set to the above lower limit value or more, there is a tendency that the effect of improving the adhesion property can be sufficiently obtained. When it is set to the above upper limit value or less, it is possible to suppress a decrease in sensitivity or a residual residue after development. And the tendency to become a defect.

When a surfactant is used, its content ratio in the total solid content of the photosensitive coloring composition is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0.01. ∼0.5% by mass, and most preferably 0.03∼0.3% by mass. When the content ratio of the surfactant is set to the above lower limit value, the smoothness and uniformity of the coating film tend to be easily exhibited. When the content ratio of the surfactant is set to the above upper limit value, the coated film is likely to be expressed. The smoothness and uniformity can also suppress the tendency of other characteristics to deteriorate.

<Physical properties of photosensitive coloring composition> The photosensitive coloring composition of the present invention can be suitably used to form a colored spacer. From the viewpoint of use as a colored spacer, it is preferable that the optical density (OD) per 1 μm film thickness of the cured film is high. The colored spacer obtained by curing the photosensitive coloring composition of the present invention is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.08 or more, and even more preferably 0.10. The above is preferably 0.15 or more. Here, the optical density (OD) per 1 μm film thickness is a value measured by the method described in the examples described below.

In the case of lamination with a blue color filter, the optical density (OD) of the two layers obtained by laminating the colored spacer and the blue color filter is preferably 0.5 or more, and more preferably 1.0. the above. Here, the optical density (OD) of the two layers of the stacked layers is a value measured by a method described in the examples described below.

The photosensitive coloring composition of the present invention preferably has a ratio of an average absorbance at a wavelength of 400 to 500 nm to an average absorbance at a wavelength of 500 to 700 nm of 1.8 or more, more preferably 2.0 or more, and further preferably 3.0 or more. In addition, it is preferably 15 or less, more preferably 10 or less, even more preferably 7 or less, and even more preferably 4.5 or less. By setting it to be more than the above-mentioned lower limit value, it is possible to obtain a hue close to black when laminated with a blue color filter. Moreover, when it is below the said upper limit, there exists a tendency for optical density (OD) to be improved.

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 can be used to form a cured film having a film thickness of 2.5 μm by using the photosensitive coloring composition. The spectrophotometer measures the absorbance at a wavelength of 400 to 700 nm at intervals of 1 nm and specifies it. The detailed measurement conditions and the like are not particularly limited, and for example, the measurement can be performed by the following method. First, a photosensitive coating composition was applied on a glass substrate ("AN100" manufactured by AGC) using a spin coater. Next, 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 irradiated with ultraviolet rays in the air. Ultraviolet light having an intensity of 32 mW / cm ² at a wavelength of 365 nm was used, and the exposure amount was set to 70 mJ / cm ² . Next, a developing solution containing 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 a water pressure of 0.15 MPa was performed at 25 ° C. After the spray development, the development was stopped by pure water, and the cleaning was performed by water washing spray. The spray development time is adjusted between 10 to 120 seconds, and is set to 1.5 times the time to dissolve and remove the unexposed coating film. The substrate with a coating film obtained by these operations was heated in an oven at 230 ° C. for 20 minutes to harden the pattern to obtain a substrate with a cured film having a film thickness of 2.5 μm. Next, a UV-3150 spectrophotometer manufactured by Shimadzu Corporation was used to measure the absorbance of the substrate at a wavelength of 400 to 700 nm at intervals of 1 nm, and a glass substrate to which the photosensitive coloring composition was not applied was used as a control. The average absorbance at a wavelength of 400 to 500 nm every 1 nm is averaged to calculate the average absorbance. Similarly, the average absorbance at a wavelength of 500 to 700 nm is calculated, and then the average absorbance at a wavelength of 400 to 500 nm is calculated with respect to the wavelength. Ratio of average absorbance at 500 to 700 nm.

In the second aspect, the chromaticity coordinates (x, y) in the xy chromaticity diagram of the photosensitive coloring composition of the present invention satisfy 0.40 ≦ x ≦ 0.55, and 0.35 ≦ y ≦ 0.50. By setting the chromaticity coordinates (x, y) within the above range, it is considered that the color tone when laminated with blue is good, and light leakage at a wavelength of 400 to 500 nm is suppressed.

x is 0.40 or more, preferably 0.42 or more, more preferably 0.45 or more, and even more preferably 0.46 or more. In addition, x is 0.55 or less, preferably 0.53 or less, more preferably 0.52 or less, even more preferably 0.51 or less, and even more preferably 0.50 or less. When it is set to the above lower limit value, sufficient light-shielding property can be ensured, and transmittance at a wavelength of 400 to 500 nm can be suppressed. When it is set to the above upper limit value, the mechanical properties tend to be improved. . The combination of the upper limit and the lower limit is, for example, preferably 0.42 to 0.53, more preferably 0.45 to 0.52, still more preferably 0.46 to 0.51, and even more preferably 0.46 to 0.50.

In addition, y is 0.35 or more, preferably 0.37 or more, more preferably 0.40 or more, still more preferably 0.41 or more, and even more preferably 0.42 or more. In addition, y is 0.50 or less, preferably 0.48 or less, more preferably 0.47 or less, even more preferably 0.46 or less, and even more preferably 0.45 or less. When it is set to the above lower limit value, sufficient light-shielding property can be ensured, and transmittance at a wavelength of 400 to 500 nm can be suppressed. When it is set to the above upper limit value, the mechanical properties tend to be improved. . The combination of the upper limit and the lower limit is, for example, preferably 0.37 to 0.48, more preferably 0.40 to 0.47, still more preferably 0.41 to 0.46, and even more preferably 0.42 to 0.45.

Here, the chromaticity coordinates (x, y) in the xy chromaticity diagram can be specified by forming a cured film having a film thickness of 1.0 μm using a photosensitive coloring composition and measuring the spectroscopic spectrum. The detailed measurement conditions and the like are not particularly limited, and for example, the measurement can be performed by the following method. First, a photosensitive coating composition was applied on a glass substrate ("AN100" manufactured by AGC) using a spin coater. Next, 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 irradiated with ultraviolet rays in the air. Ultraviolet light having an intensity of 32 mW / cm ² at a wavelength of 365 nm was used, and the exposure amount was set to 70 mJ / cm ² . Next, a developing solution containing 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 a water pressure of 0.15 MPa was performed at 25 ° C. After the spray development, the development was stopped by pure water, and the cleaning was performed by water washing spray. The spray development time is adjusted between 10 to 120 seconds, and is set to 1.5 times the time to dissolve and remove the unexposed coating film. The substrate with a coating film obtained by these operations was heated in an oven at 230 ° C. for 20 minutes to harden the pattern to obtain a substrate with a cured film having a film thickness of 1.0 μm. Next, regarding the light transmittance of the substrate, a spectrophotometer UV-3150 manufactured by Shimadzu Corporation was used to measure the transmittance at a wavelength of 380 to 780 nm at intervals of 1 nm, and the glass was not coated with the photosensitive coloring composition. The substrate served as a control. Then, according to JIS Z8701, the chromaticity coordinates (x, y) of the xy chromaticity diagram in the XYZ color system are calculated from the transmittance at a wavelength of 380 to 780 nm and the light source distribution (emission spectrum) in FIG. 1.

<The manufacturing method of a photosensitive coloring composition> The photosensitive coloring composition of this invention is manufactured according to a conventional method. In general, it is preferable to use a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like to perform a dispersion treatment on the colorant in advance. Since (a) the coloring agent is made finer by the dispersion treatment, the coating characteristics of the photosensitive coloring composition are improved.

The dispersion treatment is usually preferably performed by a system using a part or the whole of (a) a colorant, (e) a solvent, and (f) a dispersant, and optionally (b) an alkali-soluble resin (hereinafter sometimes provided in The mixture obtained by the dispersion treatment and the composition obtained by the treatment are called "ink" or "pigment dispersion"). In particular, if a polymer dispersant is used as the (f) dispersant, the obtained ink and the photosensitive coloring composition can be suppressed from thickening with time (excellent dispersion stability), and therefore, it is preferable. As described above, in the step of producing the photosensitive coloring composition, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. The (a) colorant, (e) solvent, and (f) dispersant that can be used as the pigment dispersion liquid are each preferably used as a photosensitive coloring composition and can be described by a user.

Furthermore, when a liquid containing all the components formulated in the photosensitive coloring composition is subjected to a dispersion treatment, since heat is generated during the dispersion treatment, there is a possibility that a highly reactive component may be modified. Therefore, it is preferable to perform the dispersion treatment by a system containing no (c) photopolymerization initiator or (d) ethylenically unsaturated compound. When (a) the colorant is dispersed by a sand mill, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm can be preferably used. The dispersion treatment conditions are as follows: The temperature is usually in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersing time tends to vary depending on the composition of the liquid and the size of the dispersing processing device, and it may be adjusted appropriately. The standard for dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) when the pigment dispersion liquid or the photosensitive coloring composition is applied to the substrate is in the range of 50 to 300. By setting it to the above lower limit value or more, there is a tendency that the pigment ((a) colorant) particles which are insufficiently dispersed and remain rough can be suppressed, and the developability, adhesiveness, resolvability and the like are easily changed. full. Moreover, when it is below the said upper limit, there exists a tendency which can suppress a case where a pigment breaks and a large amount of ultrafine particles generate | occur | produce, and can make dispersion stability favorable.

The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm. The particle diameter can be measured by a dynamic light scattering method or the like. Then, the ink obtained by the dispersion process and the other components contained in the photosensitive coloring composition are mixed to prepare a uniform solution. In the manufacturing steps of the photosensitive coloring composition, since fine dirt is often mixed into the liquid in many cases, it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.

[Hardened product] The hardened product of the present invention can be obtained by hardening 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.

[Colored spacer] The method for producing the colored spacer of the present invention including the cured product of the present invention will be described.

(1) Support As a support for forming a colored spacer, the material is not particularly limited as long as it has a moderate strength. Transparent substrates are mainly used. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polyfluorene. Thermoplastic resin sheets such as epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins, and various glass materials. Among them, glass and a heat-resistant resin are preferred from the viewpoint of heat resistance. In addition, transparent electrodes such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) may be formed on the surface of the substrate. In addition to a transparent substrate, it may be formed on a TFT array.

In order to improve surface properties such as adhesion, the support may be subjected to a corona discharge treatment, an ozone treatment, a thin film forming treatment of various resins such as a silane coupling agent or a urethane resin, etc., as necessary. The thickness of the transparent substrate is usually set in a range of 0.05 to 10 mm, and preferably in a range of 0.1 to 7 mm. When a thin film forming process is performed on various resins, the film thickness is usually in the range of 0.01 to 10 μm, and preferably in the range of 0.05 to 5 μm.

(2) Colored spacer The photosensitive colored composition of the present invention can be used for the same applications as the known photosensitive colored composition for a color filter. Hereinafter, the method for forming a colored spacer will be described. .

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

(3) Formation of colored spacers [1] Supply method to substrate The photosensitive colored composition of the present invention is usually supplied to a support in a state of being dissolved or dispersed in a solvent. The supply method can be performed by a conventionally known method such as a spin coating method, a bar coating method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In addition, it may be supplied in a pattern by an inkjet method, a printing method, or the like. Among them, if the die coating method is used, it is possible to greatly reduce the amount of coating liquid used, and it is not affected at all by the fog and the like attached when the spin coating method is used, and it is preferable from a comprehensive viewpoint that the generation of impurities can be suppressed.

The coating amount varies depending on the application. For example, in the case of colored spacers, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably in the range of 1 μm to 9 μm, and particularly preferably in the range of 1 μm to 7 μm range. In addition, it is important that the thickness of the dry film or the height of the spacer that is finally formed is uniform over the entire area of the substrate. When the deviation is large, there may be a case where a defect such as display unevenness occurs in the liquid crystal panel.

However, when the photosensitive coloring composition of the present invention is used to form colored spacers having different heights at one time by a photolithography method, the heights of the finally formed colored spacers are different.

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 method after the photosensitive coloring composition is supplied to the support is preferably a drying method using a hot plate, an IR (infrared) oven, or a convection oven. Further, a reduced-pressure drying method for drying in a decompression chamber without increasing the temperature may be combined.

The drying conditions such as drying temperature and drying time can be appropriately selected according to the type of the solvent component and the performance of the dryer used. It is usually selected within a temperature range of 40 ° C to 130 ° C and 15 seconds to 5 minutes, and preferably within a range of 50 ° C to 110 ° C and 30 seconds to 3 minutes.

[3] Exposure method Exposure is performed by superposing a negative mask pattern on a coating film of a photosensitive coloring composition, and irradiating a light source of ultraviolet or visible light through the mask pattern. In the case of using an exposure mask for exposure, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or arranging the exposure mask at a position away from the coating film of the photosensitive coloring composition and Method for projecting exposed light through the exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern may be used. At this time, in order to prevent the sensitivity of the photopolymerizable layer from being reduced by oxygen, it may be performed in a deoxidizing environment or after exposure to an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer as necessary.

As a preferred aspect of the present invention, in the case where the colored spacers of different heights are simultaneously formed by the photolithography method, for example, the following exposure mask is used, which has a light shielding portion (light transmittance 0%) and a plurality of The opening having the highest average light transmittance (completely transparent opening) and the opening having a low average light transmittance (middle transparent opening). According to this method, a difference in the residual film rate is generated by using a difference between the average light transmittance of the intermediate transmission opening portion and the completely transmitted opening portion, that is, a difference in exposure amount. A method of making a matrix-shaped light-shielding pattern using a light-shielding unit having a minute polygon is known as the intermediate transmission opening. In addition, a method of making the light transmittance by controlling a film of a material such as chromium-based, molybdenum-based, tungsten-based, or silicon-based materials as an absorber is known.

The light source used for the above exposure is not particularly 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 lamp, and a fluorescent lamp, or an argon ion lightning Laser, YAG (Yttrium Aluminum Garnet) laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, near-infrared semiconductor laser and other laser light sources. When using light of a specific wavelength, an optical filter can also be used.

The optical filter may be, for example, a type in which the light transmittance at the exposure wavelength can be controlled by a thin film. Examples of the material in this case include Cr compounds (oxides, nitrides, oxynitrides of Cr, Fluoride, etc.), MoSi, Si, W, Al, etc.

The exposure amount is usually 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, and usually 300 mJ / cm ² or less, and preferably 200 mJ / cm. ² or less, more preferably 150 mJ / cm ² or less. In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, and preferably 400 μm. Below, it is more preferably 300 μm or less.

[4] Development method After performing the above exposure, an image pattern can be formed on a substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye, or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic basic compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; or mono, di or triethanolamine, mono, di or trimethylamine, mono, di or tri Ethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline and other organic Basic compounds. These basic compounds may be a mixture of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl groups. Nonionic surfactants such as esters; anionic properties such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, sulfosuccinates, etc. Surfactants; Ampholytic surfactants such as alkyl betaines and amino acids.

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

The conditions for the development treatment are not particularly limited, and generally, the development temperature can be in the range of 10 to 50 ° C, preferably 15 to 45 ° C, and particularly preferably 20 to 40 ° C. By the immersion development method, the jet development method, Any development method such as a brush development method and an ultrasonic development method is performed.

[5] Additional exposure and thermal curing treatment If necessary, additional exposure may be performed on the substrate after development by the same method as the above-mentioned exposure method, and thermal curing treatment may also be performed. Regarding the heat curing treatment conditions at this time, the temperature can be selected in the range of 100 ° C to 280 ° C, preferably 150 ° C to 250 ° C, and the time can be selected in the range of 5 minutes to 60 minutes.

The size or shape of the colored spacer of the present invention is appropriately adjusted according to the specifications and the like of the color filter to which it is applied. The photosensitive coloring composition of the present invention is particularly suitable for the simultaneous formation of the spacer and the auxiliary by the photolithography method. Colored spacers having different spacer heights are useful. In this case, the height of the spacer is usually about 2 to 7 μm, and the auxiliary spacer usually has a height that is about 0.2 to 1.5 μm lower than the spacer.

[Color filter] The color filter of the present invention includes the coloring spacer of the present invention as described above, for example, a black matrix and red, green, and blue pixel color layers are laminated on a glass substrate as a transparent substrate. And surface coating, and forming an alignment film after forming colored spacers. There may be a case where a pixel colored layer and a colored spacer are formed on the liquid crystal driving side substrate, or a case where they are formed separately on a transparent substrate and a liquid crystal driving side substrate. In addition, as described in Korean Laid-Open Patent No. 10-2013-0015734, Korean Laid-Open Patent No. 10-2015-0059026, and Korean Laid-Open Patent No. 10-2017-0017447, coloring may be provided in a non-display area. In this case, the spacer can reduce the leakage of light to the non-display area by stacking a color filter of a blue layer or a red layer on the opposite side. Moreover, it may be only a blue layer, only a red layer, and only a green layer. Liquid crystal displays equipped with LED backlight devices tend to have a stronger blue light component. Therefore, the components of blue light are easily transmitted. For example, when there is only a single layer, especially a blue layer, there is a tendency that light leakage at a wavelength of 400 to 500 nm is likely to occur. The light leakage can be adjusted by the laminated structure when the liquid crystal display is manufactured, or the material characteristics of the facing colored spacer. For example, it is suitable to use a colored spacer obtained by curing the photosensitive coloring composition of the present invention.

[Image display device] The image display device of the present invention includes the colored spacer of the present invention. For example, the color filter having the colored spacer of the present invention and the liquid crystal driving side substrate can be bonded to form a liquid crystal cell, and liquid crystal can be injected into the formed liquid crystal cell, thereby manufacturing a colored spacer with the colored spacer of the present invention. The image display device of the present invention, such as a liquid crystal display device. [Example]

Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. The constituents of the photosensitive coloring composition used in the following examples and comparative examples are as follows.

<Alkali-soluble resin-I> While stirring 145 parts by mass of propylene glycol monomethyl ether acetate, the mixture was stirred, and the temperature was raised to 120 ° C. To this, 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, and the reaction was continued for 3 hours. 8.47 parts by mass of 2,2'-azobis-2-methylbutyronitrile was added dropwise, and stirring was continued at 90 ° C for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of tris (dimethylaminomethyl) phenol 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 the mixture was reacted at 100 ° C for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw of the alkali-soluble resin-I thus obtained, as measured by GPC, was 8400, and the acid value was 80 mgKOH / g.

<Alkali Soluble Resin-II> While stirring the mixed solution of 210.1 parts by mass of propylene glycol monomethyl ether acetate and 52.5 parts by mass of propylene glycol monomethyl ether, the mixture was stirred while being heated to 120 ° C. 3.52 parts by mass of benzyl methacrylate, 68.8 parts by mass of methacrylic acid, and 39.7 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto over 3 hours. 3.3 'parts by mass of 2'-azobis-2-methylbutyronitrile, and further stirred at 90 ° C for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 38.4 parts by mass of glycidyl methacrylate, 0.8 parts by mass of tris (dimethylaminomethyl) phenol, and 0.1 part by mass of hydroquinone were charged, and the reaction was continued at 100 ° C. 12 hour. The polystyrene-equivalent weight average molecular weight Mw of the alkali-soluble resin-II thus obtained, measured by GPC, was 19,100, and the acid value was 198 mgKOH / g.

<Alkali-soluble resin-III> In the presence of 1.8 parts by mass of triethylamine, 0.12 parts by mass of 4-methoxyphenol, and 91.8 parts by mass of propylene glycol monomethyl ether acetate, 17 parts by mass of succinic anhydride was made at 85 ° C. Part was reacted with 350 parts by mass of dipentaerythritol polyacrylate (A-9550 manufactured by Shin Nakamura Chemical Co., Ltd.) for 6 hours, thereby obtaining a polyfunctional acrylate (d having 1 carboxyl group and 2 or more acryl fluorenyl groups in 1 molecule) -1). Then, 32.7 g of bisphenol A epoxy resin (jER-828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186), 460.7 g of the above-mentioned polyfunctional acrylate (d-1), 2, 2, 6 at 80 ° C. , 6-tetramethylpiperidine 1-oxy radical 0.2 g, triphenylphosphine 8.0 g, and propylene glycol monomethyl ether acetate 18.9 g were stirred until the acid value became 2 mgKOH / g or less. Then, 161.6 g of propylene glycol monomethyl ether acetate was added to 520.5 g of the obtained reaction product to dissolve it, and 24.2 g of 1,2,3,6-tetrahydrophthalic anhydride was added, and reacted at 90 ° C. 4 hours, thereby obtaining alkali-soluble resin-III. The alkali-soluble resin-III obtained 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 BYK-Chemie (including A-blocks with a quaternary ammonium salt group and a tertiary amine group in the side chain and those without B-block acrylic AB block copolymer. Amine value is 70 mgKOH / g. Acid value is 1 mgKOH / g or less) The A block of the dispersant-I contains the following formulae (1a) and (2a) The repeating unit includes a repeating unit of the following formula (3a) in the B block. The content ratios of the repeating units occupied by the following formulae (1a), (2a), and (3a) in the total repeating units of the dispersant-I are 11.1 mole%, 22.2 mole%, and 6.7 mole%, respectively.

[Chemical 50]

<Dispersant-II> "DISPERBYK-2000" manufactured by BYK-Chemie (copolymerization of acrylic block AB containing an A block having a quaternary ammonium salt group in a side chain and a B block having no quaternary ammonium salt group (Amine value is 10 mgKOH / g. Acid value is less than 1 mgKOH / g)

<Solvent-I> PGMEA: propylene glycol monomethyl ether acetate <Solvent-II> MB: 3-methoxybutanol <Photopolymerization initiator-I>

OXE-01 (oxime ester photopolymerization initiator) manufactured by BASF

<Photopolymerizable monomer> DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. <Additive-I> KAYAMER PM-21 (methacryl fluorenyl-containing phosphate) manufactured by Nippon Kayaku Co., Ltd. <Additive- II ＞ SH6040 (3-glycidyloxypropyltrimethoxysilyl) manufactured by Dow Corning Toray Corporation <surfactant> MEGAFAC F-554 manufactured by DIC Corporation

<Preparation of Pigment Dispersions 1 to 6> The pigments, dispersants, alkali-soluble resins, and solvents described in Table 2 were mixed so as to have a mass ratio described in Table 2. In addition, the amounts of the dispersant and the alkali-soluble resin in Table 2 are the amounts of solid components, and the amount of the solvent also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. This solution was dispersed for 3 hours by a paint shaker in a range of 25 to 45 ° C. As beads, use 0.5 mm Zirconia beads, and add 2.5 times the mass of the dispersion. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersion liquids 1 to 6.

[Table 2]

<Preparation of Pigment Dispersion Liquid 7> The pigment dispersion liquid 7 was prepared by dispersing in the same manner as the pigment dispersion liquids 1 to 6 except that the type of pigment, the type of dispersant, and the mixing ratio of each component were changed as follows. In addition, the amount of the dispersant and the alkali-soluble resin is the amount of the solid matter component, and the amount of the solvent also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. C.I.Pigment Orange 64 70 parts by mass C.I.Pigment Purple 29 10 parts by mass C.I.Pigment Blue 16 20 parts by mass Dispersant-II 100 parts by mass Alkali-soluble resin-I 100 parts by mass Solvent-I 960 parts by mass Solvent-II 240 parts by mass

<Preparation of Photosensitive Coloring Compositions 1 to 14> [Examples 1 to 12, Comparative Examples 1 and 2] Using the pigment dispersion liquids 1 to 5 and 7 prepared as described above, the total solid content of the photosensitive coloring composition was used. Add the components such that the ratios in Tables 3 to 5 are the blending ratios, and further add a solvent such that the total solids content ratio is 22% by mass and PGMEA / MB = 80/20 (mass ratio). The mixture was stirred and dissolved to prepare a photosensitive coloring composition 1 to 14. Each of the obtained photosensitive coloring compositions was evaluated by the method described below.

[table 3]

[Table 4]

[table 5]

<Measurement of chromaticity> Each photosensitive coloring composition was applied on a glass substrate ("AN100" manufactured by AGC) using a spin coater so that the film thickness after heating and firing became 1.0 μm. Then, the 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 full exposure processing without using a photomask. Ultraviolet light having an intensity of 32 mW / cm ² at a wavelength of 365 nm was used, and the exposure amount was set to 70 mJ / cm ² . The ultraviolet irradiation was performed in the air.

Next, a developing solution containing 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 to perform a water pressure of 0.15 MPa at 25 ° C. After the spray development, the development was stopped by pure water, and the cleaning was performed by water washing spray. The shower development time was set to 50 seconds for development. The substrate was heated and fired in an oven at 230 ° C. for 20 minutes to be hardened to obtain a substrate for color measurement with a colored layer.

Using a UV-3150 spectrophotometer manufactured by Shimadzu Corporation, the light transmittance of each of the obtained chromaticity measurement substrates at a wavelength of 380 to 780 nm was measured at intervals of 1 nm. A glass substrate was used as a control. Then, calculate the chromaticity coordinates (x) of the xy chromaticity diagram in the XYZ color system based on the transmittance of every 1 nm of the wavelengths of 380 to 780 nm for each chromaticity measurement substrate and the light source distribution (luminous spectrum) in FIG. 1. , Y). The results are shown in Tables 3 to 5.

<Production of the substrate for evaluating optical characteristics> Each photosensitive coloring composition was applied on a glass substrate ("AN100" manufactured by AGC) using a spin coater so that the film thickness after heating and firing became 2.5 μm. Then, the 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 full exposure processing without using a photomask. Ultraviolet light having an intensity of 32 mW / cm ² at a wavelength of 365 nm was used, and the exposure amount was set to 70 mJ / cm ² . The ultraviolet irradiation was performed in the air.

Next, a developing solution containing 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 to perform a water pressure of 0.15 MPa at 25 ° C. After the spray development, the development was stopped by pure water, and the cleaning was performed by water washing spray. The shower development time was set to 50 seconds for development. This substrate was heated and fired in an oven at 230 ° C. for 20 minutes to be hardened to obtain a substrate for evaluating optical characteristics having a colored layer.

<Preparation of blue substrate> Using the pigment dispersion liquid 6 prepared above, each component is added so that the ratio of the total solids component of the photosensitive coloring composition becomes the following blending ratio, and the content of the total solids component is further included. PGMEA was added so that the ratio might be 22% by mass, and the mixture was stirred and dissolved to prepare a photosensitive coloring composition 15.

Pigment dispersion 6 41.67% by mass Alkali-soluble resin-I 34.98% by mass Photopolymerizable monomer 19.25% by mass Photopolymerization initiator-I 4.00% by mass Surfactant 0.10% by mass

Then, a blue substrate having a blue layer was obtained by adjusting the film thickness after heating and firing so as to be 1.0 μm, and performing the same operation as in <Preparing a substrate for evaluating optical characteristics>.

<Evaluation of transmittance, absorbance, and hue at a wavelength of 400 to 500 nm> The wavelengths of the obtained substrates for evaluating optical characteristics and blue substrates were measured using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation at a wavelength of 380 to The light transmittance and absorbance at 780 nm were compared with a glass substrate on which the photosensitive coloring composition was not applied.

Then, the measured values of the transmittances at intervals of 1 nm at a wavelength of 400 to 500 nm of each substrate are averaged to calculate the average transmittance, and the calculated values are then used to calculate the optical property evaluation substrate and the blue color. The average transmittance in the state where the substrates were overlapped was evaluated according to the following criteria. In the case where the blue substrate is alone, the average transmittance at a wavelength of 400 to 500 nm becomes high. Therefore, it is preferable to further reduce the value of the average transmittance by further laminating the 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. The results are shown in Tables 3 to 5.

(Average transmittance of wavelength 400 to 500 nm) A: 5% or less C: More than 5%

Then, the average absorbance was calculated by averaging the measured values of the absorbance at every 1 nm at the wavelengths of 400 to 500 nm of each optical property 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. These results are shown in Tables 3 to 5. In Tables 3 to 5, the value of (average absorbance at a wavelength of 400 to 500 nm) / (average absorbance at a wavelength of 500 to 700 nm) is described as the "absorbance ratio".

Next, the optical property evaluation substrate and the blue substrate were calculated based on the transmittance of every 1 nm of the wavelengths of 380 to 780 nm and the light source distribution (emission spectrum) of each of the optical property evaluation substrates and the blue substrates. The chromaticity coordinates (x, y) of the xy chromaticity diagram in the XYZ color measurement system in this state are evaluated based on the following criteria. Each result is shown in Tables 3-5.

(Tint) (1) A: x ≧ 0.25 and y ≧ 0.25 (hue is close to black) (2) B: x ≧ 0.20 and y ≧ 0.20, and does not satisfy the range of (1) (hue is slightly blue) (3 ) C: x <0.20 or y <0.20 (hue is very blue)

<Evaluation of Optical Density (OD)> The optical densities of each of the colored layer of the obtained substrate for evaluating optical characteristics and the blue layer of the blue substrate were measured by a transmission densitometer ("D200-II" manufactured by GretagMacbeth). OD). Based on these measured values, the optical density in a state where the colored layer and the blue layer are laminated is calculated. The results are shown in Tables 3 to 5. Then, the optical density (OD / μm) per unit film thickness of only the colored layer of the substrate for evaluating optical characteristics was calculated. The results are shown in Tables 3 to 5. In addition, in Tables 3 to 5, as the "optical density OD / μm", the unit optical density OD / μm per 1 μm is described.

<Preparation of a substrate for evaluating mechanical characteristics> Each of the photosensitive coloring compositions of Examples 1 to 12 and Comparative Examples 1 and 2 was coated on a glass substrate ("AN100" manufactured by Asahi Glass Co., Ltd.) using a spin coater. After vacuum drying, it was dried by heating on a hot plate at 90 ° C for 90 seconds to form a coating film. For the obtained coating film, a fully transparent opening having a circular pattern of various diameters having a diameter of 5 to 50 μm (5 to 20 μm: at intervals of 1 μm; 25 μm to 50 μm: at intervals of 5 μm) was used. Part of the exposure mask performs exposure processing. The exposure pitch (distance between the mask and the coating surface) was 250 μm. As the irradiation light, ultraviolet rays having an intensity of 32 mW / cm ² at a wavelength of 365 nm were used, and the exposure amount was set to 70 mJ / cm ² . The ultraviolet irradiation was performed in the air.

Next, a developing solution containing 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 a water pressure of 0.05 MPa was performed at 25 ° C. After the spray development, the development was stopped by pure water, and the cleaning was performed by water washing spray. The spray development time is adjusted between 10 to 120 seconds, and is set to 1.3 times the time to dissolve and remove the unexposed coating film. With these operations, a pattern that will not need to be partially removed is obtained. The patterned substrate was heated in an oven at 230 ° C. for 20 minutes to harden the pattern to obtain a substantially cylindrical spacer pattern having a height of 2.5 μm.

<Evaluation of mechanical characteristics> Among the obtained spacer patterns, a pattern having a bottom surface diameter of 22 ± 2 μm was used as an object, and the elastic recovery rate was measured in the following procedure. As a micro-hardness tester for load-unloading test, a Fischer Instruments company (FISCHERSCOPE H100C) was used, and a flat indenter with a diameter of 50 μm was used at a measurement temperature of 23 ° C. to apply a load to the spacer at a constant speed (5 mN / sec). Hold the load at 100 mN for 5 seconds, then unload it at the same speed, and hold it for 5 seconds at the load reduced to 0 mN to obtain the load-displacement curve. Based on the load-displacement curve, the maximum displacement value was taken 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]. Then, the elastic recovery rate was calculated by the following formula, and the elastic recovery rate was evaluated as follows. Each result is shown in Tables 3-5.

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

(Elastic recovery rate) A: 90% or more C: Less than 90%

Regarding the spacer pattern obtained using the photosensitive coloring composition of Examples 1, 6 to 9, and Comparative Example 2, the load reached was changed from 100 mN to 200 mN. Load and displacement curves were obtained in the order and conditions, and the elastic recovery rate was calculated. The results are shown in Table 6.

[TABLE 6]

In Table 3, according to the comparison between Examples 1 to 5 and Comparative Example 1, it can be seen that by using a photosensitive coloring composition having a content ratio of an orange pigment in all the colorants of 45% by mass or more, a wavelength of 400 to 500 nm The average transmittance becomes sufficiently low. It is considered that the reason is that by setting the content ratio of the orange pigment in all colorants to the above lower limit value, the light having a wavelength of 400 to 500 nm which is not absorbed in the blue layer and is transmitted is sufficiently blocked by the orange pigment. . In the same manner, according to the comparison between Examples 1 to 5 and Comparative Example 1, it can be seen that the chromaticity coordinates (x, y) in the xy chromaticity diagram satisfy 0.40 ≦ x ≦ 0.55 and 0.35 ≦ y ≦ 0.50. The average transmittance at a wavelength of 400 to 500 nm becomes sufficiently low. The reason is considered that by setting the chromaticity coordinates (x, y) within the above range, that is, by setting a coloring agent whose color is close to orange, the colorant can be sufficiently shielded from blue Light having a wavelength of 400 to 500 nm which is not absorbed in the layer and transmitted.

Furthermore, according to the comparison between Examples 1 to 5 and Comparative Example 1, it can be seen that when a photosensitive coloring composition having a content ratio of orange pigment in all the colorants of 45% by mass or more is used, the color tone is also practically sufficient. The reason is that by adding the tint of the colored layer to the tint of the blue layer, it becomes a uniform and nearly black tint. It is also known from the comparison between Examples 2 and 3 and Example 4 that the smaller the content ratio of the blue pigment and the purple pigment in all the colorants, the better the color tone. The reason is also to add the tint of the colored layer to the tint of the blue layer.

In Table 4, it can be seen from the comparison between Examples 6 to 9 and Comparative Example 2 that by setting the content ratio of the coloring agent in the total solid content of the photosensitive coloring composition to 23% by mass or less, The mechanical characteristics become good. It is considered that by setting the content ratio of the coloring agent in the total solids content to 23% by mass or less, the content ratio of the coloring agent that is not elastically deformed is prevented from becoming too high, and it is possible to suppress the effect of applying a load on the colored spacer. Plastic deformation and elastic recovery become good. In addition, it can be seen from the comparison of Examples 6 to 9 that regardless of the content ratio of the coloring agent in the total solid content, the content of the orange pigment in the entire colorant can be sufficiently reduced by setting the content ratio of the orange pigment to 45% by mass or more. The average transmittance at a wavelength of 400 to 500 nm.

Furthermore, according to Examples 1 to 5 of Table 3 and Examples 10 and 11 of Table 5, it can be seen that regardless of the type of the colorant contained in the orange pigment, the content ratio of the orange pigment in the colorant is set to 45. At mass% or more, the average transmittance at a wavelength of 400 to 500 nm becomes sufficiently low. In addition, it can be seen that regardless of the type of the coloring agent contained other than the orange pigment, the mechanical characteristics of the colored spacer are changed by setting the content ratio of the coloring agent in the total solid content of the photosensitive coloring composition to 23% by mass or less. Well.

Furthermore, according to a comparison between Example 1 in Table 3 and Example 12 in Table 5, it can be seen that regardless of the type of the orange pigment, the content ratio of the orange pigment in the colorant is set to 45% by mass or more, and the wavelength is 400 to 500. The average transmittance of nm can be sufficiently reduced. It was also found that regardless of the type of the orange pigment, by setting the content ratio of the coloring agent in the total solid content of the photosensitive coloring composition to 23% by mass or less, the mechanical properties of the coloring spacer are improved.

Figure 1 shows the emission spectrum of a light source used for chromaticity measurement and hue evaluation.

Claims (11)

A photosensitive coloring composition, characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound. In the total solid content of the coloring composition, the content ratio of the (a) colorant is 23% by mass or less, the colorant of the (a) colorant contains an orange pigment, and the content ratio of the orange pigment in the (a) colorant. It is 45% by mass or more. The photosensitive coloring composition according to claim 1, wherein the orange pigment contains at least one selected from the group consisting of C.I. pigment orange 13, C.I. pigment orange 43, C.I. pigment orange 64, and C.I. pigment orange 72. The photosensitive coloring composition according to claim 1 or 2, wherein the content ratio of the blue pigment and the purple pigment in the (a) colorant is 50% by mass or less. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the (a) colorant further contains a yellow pigment. The photosensitive coloring composition according to claim 4, wherein the yellow pigment contains at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, and C.I. Pigment Yellow 150. The photosensitive coloring composition according to any one of claims 1 to 5, wherein the content ratio of the (a) colorant in the total solid content of the photosensitive coloring composition is 1% by mass or more. The photosensitive coloring composition according to any one of claims 1 to 6, which is used to form a colored spacer. A photosensitive coloring composition, characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound. The coloring composition is used to form a colored spacer. In the total solid content of the photosensitive coloring composition, the content ratio of the (a) colorant is 23% by mass or less, and the chromaticity coordinates in the xy chromaticity diagram ( x, y) satisfy 0.40 ≦ x ≦ 0.55 and 0.35 ≦ y ≦ 0.50. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 8. A colored spacer comprising a hardened body as claimed in claim 9. An image display device including the colored spacer as claimed in claim 10.