TWI768074B - Photosensitive colored 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 product, coloring 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 that can be preferably used for the formation of color spacers and the like in color filters such as liquid crystal displays, and a photosensitive coloring composition obtained by curing the photosensitive coloring composition. A cured product, a colored spacer, and an image display device provided with the colored spacer. Part of the contents disclosed in the specification of 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, etc. or is incorporated herein by reference in its entirety as the disclosure of this specification.

A liquid crystal display (LCD) utilizes the property of switching the alignment of liquid crystal molecules by on/off of a voltage applied to the liquid crystal. On the other hand, each member which comprises the cell of a liquid crystal display is formed by the method using the photosensitive composition represented by the photolithography method in many cases. For reasons such as easy formation of a fine structure and easy handling of a large-area substrate, application of the photosensitive composition to a wide range is also expected in the future. In addition, the backlight device used in the liquid crystal display has the characteristics of higher resolution, lower cost, thinner appearance, etc., and now LED (Light Emitting Diode, light emitting diode) backlight device is used in the mobile terminal or TV industry. used widely.

Recently, in order to cope with the further high-definition and high-brightness of color liquid crystal displays, in active matrix liquid crystal displays, an integrated color filter in which a color filter is provided on the side of a TFT (Thin Film Transistor, thin film transistor) element substrate has been proposed. The filter method (COA method) or the integrated black matrix method (BOA method) in which only the black matrix is arranged on the substrate side of the TFT element. According to this aspect, compared with the case where the black matrix is formed on the color filter side, there is no need to keep the alignment range with the active element side, so that the aperture ratio can be increased, and as a result, high luminance can be achieved. For this type of black matrix structure, high light-shielding properties are required or light leakage in the 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 coloring integrated with a columnar spacer, a photosensitive spacer, and a black matrix has been developed to keep the distance between the two substrates in the liquid crystal display constant. spacer. As such a coloring spacer, the coloring spacer which used several organic coloring pigments as a pigment is proposed (for example, refer patent documents 1 and 2). On the other hand, as in Patent Documents 3 to 5, there are also proposed liquid crystal displays in which one or two or more color filter layers are provided in the opposing portions of the colored spacers of the frame portion. [Prior Art Literature] [Patent Literature]

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

[Problems to be Solved by Invention]

The inventors of the present invention have found that, among various panel structures, especially in liquid crystal displays equipped with LED backlight devices, a structure in which a blue color filter layer is provided at the opposite portion of the coloring spacer in the frame portion In this case, the blue light component from the LED easily permeates, and in the coloring 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, the colored spacer needs to be deformed due to external pressure during the crimping step, even if the external pressure is removed, due to the step of crimping the substrate having the colored spacer to the opposite substrate. It will also return to its original shape, that is, it needs to have mechanical properties such as elastic recovery rate.

The present invention was made in view of the above-mentioned circumstances, and an object thereof is to provide a photosensitive coloring composition capable of forming a coloring spacer having excellent mechanical properties while suppressing light leakage at a wavelength of 400 to 500 nm. [Technical means to solve problems]

The inventors of the present invention have made diligent studies to solve the above-mentioned problems, and as a result, they 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. , the above problems can be solved, and the present invention is completed. That is, the present invention has the following constitutions [1] to [11].

[1] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, And in the total solid content of the photosensitive coloring composition, the content rate of the said (a) colorant is 23 mass % or less, the said (a) colorant contains an orange pigment, and the said orange in the said (a) colorant The content ratio of the pigment is 45 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 C.I. Pigment Orange 13, C.I. Pigment Orange 43, C.I. Pigment Orange 64, and C.I. Pigment Orange 72 1 type. [3] The photosensitive coloring composition according to [1] or [2], wherein the content ratio of the blue pigment and the violet pigment in the colorant (a) 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 colorant (a) above is 1 mass in the total solid content of the photosensitive coloring composition %above.

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

[8] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, And the above-mentioned photosensitive coloring composition is used to form a coloring spacer, and in the total solid content of the photosensitive coloring composition, the content ratio of the above-mentioned (a) colorant is 23% by mass or less, and the xy chromaticity diagram is. 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 cured product according to [9]. [11] An image display device including the coloring spacer according to [10]. [Effect of invention]

According to the present invention, it is possible to provide a photosensitive coloring composition, a cured product, a coloring spacer, which can form a coloring spacer with suppressed light leakage at a wavelength of 400 to 500 nm and excellent in mechanical properties, and a drawing including such a coloring spacer. like a display device.

Hereinafter, the embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. In addition, in this invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and "(meth)acrylate" and "(meth)acryloyl group" are also the same.

The so-called "(co)polymer" means to include both homopolymer and copolymer (copolymer), the so-called "acid (anhydride)", "(anhydrous) ... acid" means to include both acid and its anhydride . Moreover, in this invention, "acrylic resin" means the (co)polymer containing (meth)acrylic acid, and the (co)polymer containing (meth)acrylate which has a carboxyl group.

In addition, in the present invention, the term "monomer" refers to the term of the so-called macromolecular substance (polymer), and its meaning includes dimer, trimer, low polymer etc. In the present invention, the term "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" refers to the weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography). In addition, in the present invention, the so-called "amine value" means the amine value in terms of effective solid content unless otherwise specified, and is represented by the amount of alkali per 1 g of the dispersant in the solid content and the mass of KOH equivalent. value. In addition, the measurement method is demonstrated below. On the other hand, the so-called "acid value" means the acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.

In addition, in this specification, the percentage or part represented by "mass" and the percentage or part represented by "weight" have the same meaning. In addition, in this specification, the specific example of a pigment may be represented by a pigment number, and the term, such as "C.I. Pigment Red 2", means a 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 , may further contain adhesion improvers such as silane coupling agents, surfactants (coatability improvers), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, development improvers, ultraviolet absorbers, anti- As for other preparation components such as an oxidizing agent, each preparation component is 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 above-mentioned (a) colorant is 23% by mass or less, and the above-mentioned (a) colorant contains Orange pigment, and the content ratio of the said orange pigment in the said (a) coloring agent is 45 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 coloring spacer, and in the total solid content of the photosensitive coloring composition, the above-mentioned (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 of the photosensitive coloring composition of the first aspect and the photosensitive coloring composition of the second aspect.

<(a) Colorant> The (a) colorant contained in the photosensitive coloring composition of the present invention is a component for coloring the 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 of the first aspect, (a) the colorant contains an orange pigment, and the content ratio of the above-mentioned orange pigment in the (a) colorant is 45% by mass or more. Since the orange pigment has a maximum wavelength of absorption peak near the wavelength of 440-490 nm in the absorption spectrum, it is considered that the light leakage at the wavelength of 400-500 nm can be effectively reduced by containing the orange pigment, especially by incorporating the orange pigment When the content ratio is more than the above lower limit value, the 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 that it is easy to increase the optical density (OD). On the other hand, since there is little absorption below the wavelength of 400 nm, there is little overlap with the absorption band of the photopolymerization initiator, which is also effective from the viewpoint of photocurability and sensitivity.

Examples of orange pigments include: C.I. 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, C.I. Pigment Orange 13, 43, 64, and 72 are preferably used in terms of dispersibility and light-shielding properties, and when the photosensitive coloring composition is cured by ultraviolet rays, it is preferable to use the ultraviolet absorptivity The lower ones are used as the orange pigment, and from this viewpoint, C.I. Pigment Orange 64 and 72 are more preferably used, and C.I. Pigment Orange 64 is particularly preferred.

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

(a) The coloring agent may contain coloring agents other than the orange pigment (hereinafter abbreviated as "other coloring agents"). Pigments and dyes are mentioned as other colorants, and pigments are preferred from the viewpoint of heat resistance, and organic pigments are preferred from the viewpoints of color tone, photocurability, and sensitivity.

Examples of the pigment include organic colored pigments such as yellow pigments, red pigments, blue pigments, purple pigments, green pigments, and brown pigments. Examples of yellow pigments include: C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 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 them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferred, and C.I. 150, C.I. Pigment Yellow 139 is particularly preferred from the viewpoint of light-shielding properties.

Examples of red pigments include: C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53: 1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 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, from the viewpoint of light-shielding property and dispersibility, C.I. Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 is preferably used. , and more preferably C.I. Pigment Red 177, 209, 224, 254. Furthermore, it is preferable to use C.I. Pigment Red 177, 254, and 272 in terms of dispersibility and light-shielding properties, and when the photosensitive coloring composition is cured by ultraviolet rays, it is preferable to use a higher ultraviolet absorptivity. The lower one is used as a red pigment, and it is more preferable to use C.I. Pigment Red 254 and 272 from this viewpoint.

Examples of blue pigments include: C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 , 79. Among them, from the viewpoint of light-shielding properties, preferred examples include: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60, and more preferred examples include: C.I. Pigment Blue 15:6, 16. Furthermore, it is preferable to use C.I. Pigment Blue 15:6, 16, 60 from the viewpoint of dispersibility or light-shielding property, and when the photosensitive coloring composition is cured by ultraviolet rays, it is preferable to use ultraviolet absorber It is more preferable to use C.I. Pigment Blue 60 from this viewpoint as a blue pigment with a lower ratio. On the other hand, as described in Korean Patent Application Publication No. 10-1840984, it is preferable to use C.I. Pigment Blue 16 from the viewpoints of reliability, light-shielding properties, and elastic recovery rate.

Examples of purple pigments include: C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, from the viewpoint of light-shielding properties, C.I. Pigment Violet 19 and 23 are preferably used, and C.I. Pigment Violet 23 is more preferably used. On the other hand, from the viewpoint of dispersibility, C.I. Pigment Violet 29 is preferably used.

Examples of green pigments include: C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. Among them, from the viewpoint of dispersibility, C.I. Pigment Green 7 and 36 are preferred.

As brown pigments, C.I. Pigment Brown 23, 25, 26, 28, 38, 41, 83, 93 can be exemplified. Among them, C.I. Pigment Brown 26, 28, 83, and 93 are preferably mentioned from the viewpoint of 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 in terms of having an absorption band in the vicinity of a wavelength of 400 to 500 nm. In the case of containing a yellow pigment, the content ratio of the yellow pigment in the (a) colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, 20 mass % or more is especially preferable, and 50 mass % or less is preferable, 40 mass % or less is more preferable, 35 mass % or less is further more preferable, and 30 mass % or less is especially preferable. By making it more than the said lower limit, the transmittance of wavelength 400-500 nm tends to become low, and it exists in the tendency for optical density (OD) to become high by making it less than the said upper limit. The combination of the upper limit and the lower limit is, for example, preferably 1 to 50 mass %, more preferably 5 to 50 mass %, still more preferably 10 to 40 mass %, still more preferably 20 to 35 mass %, particularly preferably 20 ~30% by mass.

In the case of containing a red pigment, the content ratio of the red pigment in the (a) colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more, 10 mass % or more is especially preferable, and 40 mass % or less is preferable, 30 mass % or less is more preferable, 20 mass % or less is still more preferable, 15 mass % or less is especially preferable. By making it more than the said lower limit, there exists a tendency for an optical density (OD) to become high, and it exists in the tendency for the transmittance of wavelength 400-500 nm to become low by making it equal to or less than the said upper limit. 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, particularly preferably 10 to 10% by mass. 15% by mass.

Moreover, it is preferable that the content ratio of organic coloring pigments other than a yellow pigment and a red pigment, for example, a blue pigment and a violet pigment is low from the viewpoint of a hue. From this viewpoint, (a) the total content ratio of the blue pigment and the violet pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, especially 20 mass % or less is preferable, and 0 mass % is preferable. That is, it is preferable that the blue pigment and the purple pigment are not contained in the (a) colorant.

(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, particularly preferably 20% by mass or less, and most preferably 0 quality%. By setting it below the said upper limit, there exists a tendency for a favorable color tone.

(a) The content ratio of the purple pigment in the colorant is preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 30 mass % or less, particularly preferably 20 mass % or less, and most preferably 0 mass % %. By setting it below the said upper limit, there exists a tendency for a favorable color tone.

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, (a) the total content ratio of the blue pigment and the violet pigment in the colorant is preferably 2 mass % or more, more preferably 5 mass % or more, further preferably 8 mass % or more, particularly preferably It is 10 mass % or more, and is preferably 50 mass % or less, more preferably 40 mass % or less, still more preferably 30 mass % or less, still more preferably 20 mass % or less, particularly preferably 15 mass % or less. By making it more than the said lower limit, there exists a tendency for an optical density (OD) to become high, and it exists in the tendency for the transmittance of wavelength 400-500 nm to become low by making it equal to or less than the said upper limit. The combination of the upper limit and the lower limit is, for example, preferably 2 to 50 mass %, more preferably 5 to 40 mass %, still more preferably 8 to 30 mass %, still more preferably 10 to 20 mass %, particularly preferably 10 ~15% by mass.

Moreover, you may contain a black pigment as another coloring agent. As a black pigment, an organic black pigment or an inorganic black pigment is mentioned. Examples of organic black pigments include compounds selected from the group consisting of compounds represented by the following formula (1), geometric isomers of the compounds, salts of the compounds, and salts of the geometric isomers of the compounds. at least one of the organic black pigments.

[hua 1]

In formula (1), R ¹ and R ⁶ are independently 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 R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and at least one combination of R ⁹ and R ¹⁰ in the group consisting of or NR ¹¹ bridges to bond with each other; R ¹¹ and R ¹² are independently alkyl with 1 to 12 carbons, cycloalkyl with 3 to 12 carbons, alkenyl with 2 to 12 carbons, and 3 to 12 carbons. cycloalkenyl or alkynyl with 2 to 12 carbon atoms.

The geometric isomers of the compounds represented by the general formula (1) have the following core structures (wherein the substituents in the structural formula are omitted), and the most stable ones are probably trans-trans isomers.

[hua 2]

When the compound represented by the general formula (1) is anionic, it is preferably by any known suitable cation, such as metal, organic, inorganic or metal-organic cations, specifically alkali metals, alkaline earth metals, Transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or salts formed by organometallic complexes to compensate for their charge. Moreover, when the geometric isomer of the compound represented by general formula (1) is anionic, the same salt is preferable.

Among the substituents of the general formula (1) and the definitions thereof, since the shielding ratio tends to increase, the following are preferable. The reason for this is that the following substituents are considered non-absorbing 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 more 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, SO ₃ H or SO ₃ ⁻ , more preferably a hydrogen atom or SO ₃ H.

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

Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-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.

Examples of cycloalkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, and thujyl. , norpinyl, norcaryl, norcaryl, carbenyl, pyridyl, norpinyl, pinyl, 1-adamantyl or 2-adamantyl.

Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, and 1,3-butanedi Alken-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-pyridyl-1-buten-3-yl, 2-methyl-3-butene-2- , 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

Examples of cycloalkenyl groups having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, and 3-cyclohexen-1-yl base, 2,4-cyclohexadien-1-yl, 1-p-pyren-8-yl, 4(10)-thujene-10-yl, 2-northene-1-yl, 2, 5-nor𦯉dien-1-yl, 7,7-dimethyl-2,4-norcuradien-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, 2-methyl-3-butyn-2-yl base, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn -1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyne -9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

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

The above-mentioned organic black pigment is preferably a compound represented by the following general formula (2) and/or a geometric isomer of the above-mentioned compound, more preferably a compound represented by the following general formula (2).

[hua 3]

As a specific example of such an organic black pigment, the following trade name is mentioned: Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation). The organic black pigment is preferably used by dispersing it by the dispersant, solvent and method described below. In addition, if there is a sulfonic acid derivative of the compound represented by the above general formula (1) or a sulfonic acid derivative of the above compound, especially a sulfonic acid derivative of the compound represented by the above general formula (2) or the above The sulfonic acid derivatives of the geometric isomers of the compounds may improve dispersibility or storage properties. In addition, as the organic black pigment, from the viewpoint of optical properties and reliability, it is preferable to use the organic black pigment described in Korean Laid-Open Patent Publication No. 10-2018-0052502, or Korean Laid-Open Patent Publication No. 10-2018-0052864 The organic black pigment described in the official gazette.

Moreover, as other organic black pigments, aniline black, cyanine black, perylene black, etc. can also be mentioned. Moreover, carbon black as an inorganic black pigment can also be used. As an example of carbon black, the following carbon black is mentioned.

Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B manufactured by Degussa: 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 Manufacturing: Monarch (registered trademark, the 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 PEARL S480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8 Birla company: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000

Carbon black can also be used which is covered with resin. When carbon black coated with resin is used, there is an effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black coated with the resin, for example, carbon black described in Japanese Patent Laid-Open No. 09-71733, etc. can be suitably used. In terms of volume resistance or dielectric constant, resin-coated carbon black can be suitably used.

These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the reference 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 the value calculated|required from the pigment particle diameter measured by dynamic light scattering (Dynamic Light Scattering, DLS). The particle size measurement is carried out on a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2 mass %. However, if there is a concentration recommended by the measuring machine, follow the concentration) at 25°C. to measure.

Moreover, as another coloring agent, in addition to the said pigment, a dye can also be used. Examples of dyes usable as other colorants include azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinoneimine-based dyes, quinoline-based dyes, nitro-based dyes, carbonyl-based dyes, and methine-based dyes. Base dyes, etc. Examples of azo dyes include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, C.I. Mordant Black 7, etc.

Examples of anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60 and so on. In addition, examples of phthalocyanine-based dyes include C.I. Pad Blue 5, and examples of quinoneimine-based dyes include C.I. Basic Blue 3, C.I. Basic Blue 9, and the like, and examples of quinoline-based dyes include C.I. Basic Blue 3 and C.I. Basic Blue 9. C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, etc. Examples of nitro-based dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42, and the like.

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

For example, a red pigment and a yellow pigment are used as (a) colorants, and the content ratio is adjusted so that the chromaticity coordinates (x, y) satisfy the above-mentioned range. Also, the combination of red pigment, yellow pigment and purple pigment; the combination of brown pigment and yellow pigment; the combination of brown pigment, yellow pigment and purple pigment; the combination of orange pigment and yellow pigment; the combination of orange pigment and red pigment Combination; combination of orange pigment, yellow pigment and red pigment; combination of orange pigment and violet pigment; combination of orange pigment and blue pigment; combination of orange pigment, blue pigment and violet pigment. In addition, those listed in the above-mentioned first aspect can also be applied.

Table 1 shows specific examples of pigment types and their content ratios whose chromaticity coordinates (x, y) satisfy the above-mentioned ranges, and the values of chromaticity coordinates (x, y) in each specific example. In addition, the content rate of the pigment in a table|surface is the value in the total solid content of the 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-based resin, acrylic acid resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolak-based resins, polyvinylphenol-based resins, etc. Among them, from the viewpoint of excellent plate-making properties, ( b1) Epoxy (meth)acrylate resin (b2) Acrylic resin. These may be used alone, or a plurality of them may be used in combination.

<(b1) Epoxy (meth)acrylate-based resin> (b1) Epoxy (meth)acrylate-based resin is composed of epoxy resin (epoxy compound), α,β-unsaturated monocarboxylic acid and/ Or a resin obtained by reacting the hydroxyl group generated by the reaction of the reactant of the α,β-unsaturated monocarboxylic acid ester having a carboxyl group with a polybasic acid and/or an anhydride thereof. Moreover, before making the said polybasic acid and/or its anhydride react with the hydroxyl group, it is made to react with the compound having two or more substituents which can react with the said hydroxyl group, and then the polybasic acid and/or its anhydride are reacted The obtained resin is also included in the above-mentioned (b1) epoxy (meth)acrylate resin.

Moreover, the resin obtained by making the carboxyl group of the resin obtained by the said reaction react with the compound which has a reactive functional group is also contained in the said (b1) epoxy (meth)acrylate resin. As described above, epoxy (meth)acrylate-based resins do not substantially have epoxy groups in chemical structure, and are not limited to "(meth)acrylates", since epoxy compounds (epoxy resins) are raw material, and "(meth)acrylate" is a representative example, so it is named according to the usual practice.

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

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

Here, the term "epoxy resin" includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. Moreover, the compound obtained by making a phenolic compound and an epihalohydrin react can be used for an epoxy resin. As a phenolic compound, the compound which has a divalent or more phenolic hydroxyl group is preferable, and a monomer may be sufficient as it, and a polymer may be sufficient as it. As the types of epoxy resins used as raw materials, cresol novolac epoxy resins, phenol novolak epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, trisphenol methane can be suitably used type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin which is the reaction product of the addition polymerization reactant of dicyclopentadiene and phenol or cresol and epihalohydrin , an adamantyl group-containing epoxy resin, a pyranyl epoxy resin, etc., those having an aromatic ring in the main chain can be suitably used.

In addition, as specific examples of epoxy resins, for example, bisphenol A-type epoxy resins (for example, "jER (registered trademark, the same hereinafter)-828", "jER-1001", "jER-1001", "jER-1001", " 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" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C, etc.), 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, para) cresol novolak epoxy resins (such as "EOCN ( Registered trademark, the same below)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (such as "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenol methane Type epoxy resin (such as "EPPN (registered trademark, the same below)-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resin ("EPPN-503" manufactured by Daicel Corporation Celloxide (registered trademark, the same below) 2021P", "Celloxide EHPE"), epoxy resin obtained by glycidylation of a phenol resin obtained by the reaction of dicyclopentadiene and phenol (for example, manufactured by DIC Corporation "EXA-7200", "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (B1) to (B4), etc. Specifically, as the epoxy resin represented by the following general formula (B1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd. can be mentioned, and as the epoxy resin represented by the following general formula (B2), there can be mentioned "NC-3000" manufactured by Nippon Kayaku Co., Ltd., "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., etc., can be mentioned as the epoxy resin represented by the following general formula (B4).

[hua 4]

In the above general formula (B1), a is an average value and represents a number from 0 to 10, and 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 group, naphthyl, or biphenyl. In addition, the plurality of R ¹¹¹ present in one molecule may be the same or different, respectively.

[hua 5]

In the above general formula (B2), b is an average value, representing a number from 0 to 10, and 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 group, naphthyl, or biphenyl. In addition, the plurality of R ¹²¹ present in one molecule may be the same or different, respectively.

[hua 6]

In the above 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, it contains more than one adamantane structure in the molecular structure.

[hua 7]

In the above general formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an optionally substituted adamantyl group, a hydrogen atom, and an optionally substituted carbon In the alkyl group of numbers 1 to 12, or the phenyl group which may have a substituent, * represents a bond.

[hua 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 group having 1 to 4 carbon atoms or a halogen atom, and R ¹⁴³ and R ¹⁴⁴ are each independently 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 the epoxy resin represented by any one of general formula (B1)-(B4).

Examples of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, Monocarboxylic acids such as p-vinylbenzoic acid, α-halogenated alkyl, alkoxy, halogen, nitro, and cyano substituents of (meth)acrylic acid; 2-(meth)acryloyloxyethyl succinate , 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl phthalate Ethyl ester, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl succinate, 2-(meth)acryloyloxy adipic acid Propyl ester, 2-(meth)acryloyloxypropyl tetrahydrophthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(methyl) maleate Acryloyloxypropyl, 2-(meth)acrylooxybutyl succinate, 2-(meth)acrylooxybutyl adipate, 2-(methyl)hydrophthalate Acryloyloxybutyl ester, 2-(meth)acryloyloxybutyl phthalate, 2-(meth)acryloyloxybutyl maleate (meth); addition to acrylic acid Monomers made from lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; or hydroxyalkyl p-(meth)acrylate, pentaerythritol tris(methyl) ) Monomers obtained by adding succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride) and other acids (anhydrides) to acrylate, dipentaerythritol penta(meth)acrylate; ( Meth)acrylic acid dimer, etc. Among these, in terms of sensitivity, (meth)acrylic acid is particularly preferred.

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

Furthermore, epoxy resin, α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used alone, or two or more kinds may be used together. use together. The use amount of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin, More preferably, it is the range of 0.7-1.1 equivalent. By setting the amount of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to be more than the above-mentioned lower limit value, the insufficiency of the introduction amount of unsaturated group can be suppressed. , it is easy to make the subsequent reaction with the polybasic acid and/or its anhydrides also sufficient. On the other hand, by setting the above upper limit value or less, it can be seen that the remaining unreacted products of α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and it is easy to Tendency to improve hardening properties.

Examples of the polybasic acid and/or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and pyromellitic acid. , trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloro bridge acid, methyltetrahydrophthalic acid, biphenyltetrahydrophthalic acid One or two or more of carboxylic acids, anhydrides of these, and the like.

Preferably maleic acid, succinic acid, itonic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxyl acid, or anhydrides of these. Especially preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

Regarding the addition reaction of the polybasic acid and/or its anhydride, a well-known method can also be used. The reaction of the monocarboxylate was continued under the same conditions to obtain the target product. The addition amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the produced carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH/g, and more preferably To the extent that it is in the range of 20 to 140 mgKOH/g. By setting it as the said lower limit or more, there exists a tendency for alkali developability to become favorable, and it exists in the tendency for hardenability to become favorable by setting it as the said upper limit or less.

In addition, polyalcohols, such as trimethylolpropane, pentaerythritol, and dipentaerythritol, can be added in the addition reaction of this polybasic acid and/or its anhydride, and it can be set as what introduce|transduced a multi-branched structure.

Carboxyl-containing epoxy (meth)acrylate resins are usually prepared by reacting epoxy resins with α,β-unsaturated monocarboxylic acids and/or α,β-unsaturated monocarboxylic acid esters with carboxyl groups After mixing polybasic acid and/or its anhydride, or mixing polybasic acid 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 polyhydric alcohol is not particularly limited. By heating, polybasic acids and/or their anhydrides are present in the mixture of epoxy resins and α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with carboxyl groups and polyols Any hydroxyl group undergoes an addition reaction.

Examples of the carboxyl group-containing epoxy (meth)acrylate resin include, in addition to the above, Korean Patent Publication No. 10-2013-0022955, Korean Registered Patent No. 10-0965189, and Japanese Patent Laid-Open No. 10-2013-0022955. Those described in Laid-Open Publication No. 2005-165294, Japanese Patent Laid-Open No. 2006-312704, and the like.

The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, more preferably 2500 or more, and usually 10000 or less, preferably 8000 or less, more preferably 6000 or less, still more preferably 5000 or less, particularly preferably 4000 or less. By setting the above lower limit value or more, the solubility in the developer solution tends to be suppressed from becoming too high, and by setting the above upper limit value or less, the solubility in the developer solution tends to be good. . As a combination of an upper limit and a lower limit, for example, 1000-10000 are preferable, 1500-8000 are more preferable, 2000-6000 are more preferable, 2500-5000 are still more preferable, 2500-4000 are especially preferable.

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 more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, particularly preferably 50 mgKOH/g or less. By setting it as the said lower limit or more, there exists a tendency for moderate development solubility to be obtained, and by setting it as below the said upper limit value, it exists in the tendency which can suppress that an image is melt|dissolved by developing too much. 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 particularly preferably 20 to 50 mgKOH/g.

Although the chemical structure of epoxy (meth)acrylate resin (b1) is not particularly limited, for example, epoxy (meth)acrylate resin having a partial structure (1) represented by the following general formula (I) can be mentioned. Resin (b1-A) (Hereinafter, it may be abbreviated as "epoxy (meth)acrylate resin (b1-A)"). Since the epoxy (meth)acrylate-based resin (b1-A) has three or more (meth)acryloyloxy groups in the partial structure represented by the formula (I), the ethylenic bismuth in one molecule of the resin is There is a large amount of bonds, and when a photosensitive coloring composition containing the resin is used to form a coloring spacer, the crosslinking density becomes high, and the elution of impurities to the solvent can be suppressed to ensure high reliability. The crosslinking density becomes high, whereby the mechanical properties improve.

(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 optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted aromatic ring group, l and m each independently represent an integer of 0 to 12, n represents an integer of 3 or more, ﹡ indicates a bond key.

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

Specific examples of the alkylene group include a methylene group, an ethylidene group, a propylidene group, a butylene group, and a cyclohexylene group, and from the viewpoint of compatibility with other components, a methylene group or a Ethylene group, more preferably methylene group.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, and the like, and from the viewpoint of ease of synthesis, preferred are Not substituted.

(R ⁴ ) In the above general formula (I), R ⁴ represents an n+1-valent linking group. The chemical structure of the n+1-valent linking group is not particularly limited, and an n+1-valent hydrocarbon group which may have a substituent is exemplified. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but from the viewpoint of developability, an aliphatic hydrocarbon group is preferred. Also, 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 above formula (I), R ⁷ represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted divalent aromatic ring group.

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

Specific examples of the alkylene group include a methylene group, an ethylidene group, a propylidene group, a hexylene group, and a cyclohexylene group. Preferred is an ethyl extension.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, and the like, and from the viewpoint of curability, non- superseded.

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

Specific examples of alkenylene groups include vinylidene groups, propenylene groups, butenylene groups, and cyclohexenylene groups, and from the viewpoint of curability, vinylidene groups or cyclohexenylene groups are preferred. , more preferably vinyl.

Examples of the substituent which the alkenylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, and the like, and from the viewpoint of curability, non- superseded.

As a divalent aromatic ring group in R< ⁷ >, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less, particularly preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

環、聯三伸苯環、苊環、螢蒽環、茀環等基。 又，作為二價芳香族雜環基中之雜芳香環，可為單環，亦可為縮合環。作為二價芳香族雜環基，例如可列舉具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等基。 二價芳香族環基中，就光硬化性之觀點而言，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。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 having two free valences, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,

ring, bi-triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring and other bases. Moreover, as a heteroaromatic ring in a divalent aromatic heterocyclic group, a monocyclic ring may be sufficient as it, and a condensed ring may be sufficient as it. Examples of the divalent aromatic heterocyclic group include a furan ring having two free valences, 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, furopyrrole ring, furofuran ring, thienofuran ring, benzene Isoxazole, benzisothiazole, benzimidazole, pyridine, pyridine, pyridine, pyrimidine, tris, quinoline, isoquinoline, quinoline, quinoline oxoline ring, phenanthrene ring, benzimidazole ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Among the divalent aromatic ring groups, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

As a substituent which a divalent aromatic ring group may have, an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, etc. are mentioned. Among these, from the viewpoint of sclerosing properties, unsubstituted is preferable.

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 still more preferably an ethylene group.

(l and m) In the above general formula (I), l and m each independently represent an integer of 0 to 12. From the viewpoint of developing adhesiveness, it is preferably 0 or more, more preferably 1 or more, and from the viewpoint of curability, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, More preferably, it is 2 or less. On the other hand, from the viewpoint of curability, 0 is preferable.

(n) In the above general formula (I), n represents an integer of 3 or more. n is preferably 4 or more, more preferably 5 or more, more preferably 10 or less, more preferably 8 or less, still more preferably 7 or less, particularly preferably 6 or less. By setting it as the said lower limit or more, there exists a tendency for sclerosis|hardenability to become favorable, and it exists in the tendency for image development solubility to become favorable by setting it as the said upper limit or less. The combination of the upper limit and the lower limit is, for example, preferably 4-10, more preferably 4-8, still more preferably 4-7, particularly preferably 4-6.

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

[Chemical 11]

In the above formula (II), R ⁸ represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted aromatic ring group, and * represents a bond.

(R ⁸ ) In the above formula (II), R ⁸ represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted divalent aromatic ring group.

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

Specific examples of the alkylene group include a methylene group, an ethylidene group, a propylidene group, a hexylene group, and a cyclohexylene group. Preferred is an ethyl extension.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, and the like, and from the viewpoint of curability, non- superseded.

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

Specific examples of alkenylene groups include vinylidene groups, propenylene groups, butenylene groups, and cyclohexenylene groups, and from the viewpoint of curability, vinylidene groups or cyclohexenylene groups are preferred. , more preferably cyclohexenyl.

Examples of the substituent which the alkenylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, and the like, and from the viewpoint of curability, non- superseded.

As a divalent aromatic ring group in R< ⁸ >, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less, particularly preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

環、聯三伸苯環、苊環、螢蒽環、茀環等基。 又，作為二價芳香族雜環基中之雜芳香環，可為單環，亦可為縮合環。作為二價芳香族雜環基，例如可列舉具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等基。該等中，就光硬化性之觀點而言，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。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 having two free valences, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,

ring, bi-triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring and other bases. Moreover, as a heteroaromatic ring in a divalent aromatic heterocyclic group, a monocyclic ring may be sufficient as it, and a condensed ring may be sufficient as it. Examples of the divalent aromatic heterocyclic group include a furan ring having two free valences, 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, furopyrrole ring, furofuran ring, thienofuran ring, benzene Isoxazole, benzisothiazole, benzimidazole, pyridine, pyridine, pyridine, pyrimidine, tris, quinoline, isoquinoline, quinoline, quinoline oxoline ring, phenanthrene ring, benzimidazole ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

As a substituent which a divalent aromatic ring group may have, an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, etc. are mentioned. Among these, from the viewpoint of sclerosing properties, unsubstituted is preferable.

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

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

[Chemical 12]

(Partial structure (3)) Furthermore, 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 above formula (III), R ⁹ represents an epoxy resin residue, p represents an integer of 1 or more, and * represents a bond.

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

(p) In the above formula (III), p represents an integer of 1 or more. It is preferable that p is 2 from a viewpoint of making both hardenability and developing solubility. On the other hand, from the viewpoint of curability, p is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, and from the viewpoint of developing solubility, preferably 20 or less, more preferably Preferably it is 15 or less, More preferably, it is 12 or less. By setting it as the said lower limit or more, there exists a tendency for sclerosis|hardenability to become favorable, and it exists in the tendency for image development solubility to become favorable by setting it as the said upper limit or less.

(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 developing solubility ( 3-1).

[Chemical 14]

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

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

Specific examples of alkylene groups include methylene group, ethylidene group, propylidene group, butylene group, hexylene group, cyclohexylene group, heptene group, octylene group, dodecylene group, and hardening From the viewpoint of properties, a methylene group or a propylidene group is preferable, and a propylidene group is more preferable.

Examples of the substituent which the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, a carboxyl group, and the like, and from the viewpoint of curability, non- superseded. When it has a substituent, the number of objects is not limited, One may be sufficient as it, or two or more may be sufficient.

Moreover, when the two hydrogen atoms which the methylene group ( _-CH2- ) in an alkylene group has are both substituted by a substituent, the two substituents may be connected to each other to form a hydrocarbon ring. Specific examples of γ in this case include a group represented by the following formula (IV) and a group represented by the following formula (V). * in the chemical formula represents a bond.

[Chemical 15]

Moreover, as an arbitrary substituent which the benzene ring in 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. In addition, when the benzene ring in the above formula (III-1) has a substituent, the two benzene rings in the formula (III-1) may be linked 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 more preferably a propylidene group.

(Partial structure (3-2)) The partial structure (3) represented by the above 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 above formula (III-2), * represents a bonding bond. The benzene ring in the above formula (III-2) may be further substituted by any substituent.

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

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

[Chemical 17]

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

(R ¹⁰ ) In the above 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 formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

The divalent aliphatic group includes linear, branched, cyclic, and a combination of these. Among these, from the viewpoint of developing solubility, a linear one is preferable, and on the other hand, from a viewpoint of developing adhesiveness, a cyclic one is preferable. The number of carbon atoms 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 still more preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

Specific examples of the divalent straight-chain aliphatic group include a methylene group, an ethylidene group, an n-propylidene group, a n-butylene group, a n-hexyl group, and a n-heptide group. Among these, a methylene group is preferable from a sclerosing viewpoint. Specific examples of the divalent branched-chain aliphatic group include the above-mentioned divalent straight-chain aliphatic groups having methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl Butyl, 2-butyl, 3-butyl, etc. are used as the structure of the side chain. The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norxane ring, an isoxane ring, and an adamantane ring. A base formed by removing 2 hydrogen atoms from a ring such as this. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

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; a carboxyl group, and the like. Among them, unsubstituted is preferable from the viewpoint of ease of synthesis.

Moreover, as a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The number of carbon atoms 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 still more preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

環、聯三伸苯環、苊環、螢蒽環、茀環等基。 又，作為二價芳香族雜環基中之雜芳香環，可為單環，亦可為縮合環。作為二價芳香族雜環基，例如可列舉具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等基。 該等中，就光硬化性之觀點而言，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。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 having two free valences, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,

ring, bi-triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring and other bases. Moreover, as a heteroaromatic ring in a divalent aromatic heterocyclic group, a monocyclic ring may be sufficient as it, and a condensed ring may be sufficient as it. Examples of the divalent aromatic heterocyclic group include a furan ring having two free valences, 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, furopyrrole ring, furofuran ring, thienofuran ring, benzene Isoxazole, benzisothiazole, benzimidazole, pyridine, pyridine, pyridine, pyrimidine, tris, quinoline, isoquinoline, quinoline, quinoline oxoline ring, phenanthrene ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

As a substituent which a divalent aromatic ring group 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. Among these, from the viewpoint of sclerosing properties, unsubstituted is preferable.

Moreover, as a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and one or more can be mentioned. A group formed by linking the above-mentioned divalent aromatic ring groups. 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. By setting it as the said lower limit or more, sclerosis|hardenability tends to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as said upper limit or less. 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. By setting it as the said lower limit or more, sclerosis|hardenability tends to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as said upper limit or less.

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

[Chemical 18]

As described above, the benzene ring in formula (III-3) may be further substituted with any substituent. As this substituent, 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. Among these, from the viewpoint of sclerosing properties, unsubstituted is preferable.

(Partial structure (3-4)) The partial structure (3) represented by the general formula (III) above preferably contains a partial structure ( 3-4).

[Chemical 19]

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

As γ in the above formula (III-4), those described as γ in the above formula (III-1) can be preferably used. In addition, as the optional substituent which the benzene ring in the above formula (III-4) may have, those described as the optional substituent which the benzene ring in the above formula (III-1) may have can be preferably used.

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

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

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

[hua 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 bond. The benzene ring in formula (i) may be further substituted with any substituent.

[Chemical 21]

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

(R ^b ) In the above 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 formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

The divalent aliphatic group includes linear, branched, cyclic, and a combination of these. Among these, from the viewpoint of developing solubility, a linear one is preferable, and on the other hand, from a viewpoint of developing adhesiveness, a cyclic one is preferable. The number of carbon atoms 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 still more preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

Specific examples of the divalent straight-chain aliphatic group include a methylene group, an ethylidene group, an n-propylidene group, a n-butylene group, a n-hexyl group, and a n-heptide group. Among these, a methylene group is preferable from a sclerosing viewpoint. Specific examples of the divalent branched-chain aliphatic group include the above-mentioned divalent straight-chain aliphatic groups having methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl Butyl, 2-butyl, 3-butyl, etc. are used as the structure of the side chain. The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norxane ring, an isoxane ring, and an adamantane ring. A base formed by removing 2 hydrogen atoms from a ring such as this. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

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; a carboxyl group, and the like. Among them, unsubstituted is preferable from the viewpoint of ease of synthesis.

Moreover, as a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The number of carbon atoms 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 still more preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

環、聯三伸苯環、苊環、螢蒽環、茀環等基。 又，作為二價芳香族雜環基中之雜芳香環，可為單環，亦可為縮合環。作為二價芳香族雜環基，例如可列舉具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等基。該等中，就光硬化性之觀點而言，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。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 having two free valences, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,

ring, bi-triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring and other bases. Moreover, as a heteroaromatic ring in a divalent aromatic heterocyclic group, a monocyclic ring may be sufficient as it, and a condensed ring may be sufficient as it. Examples of the divalent aromatic heterocyclic group include a furan ring having two free valences, 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, furopyrrole ring, furofuran ring, thienofuran ring, benzene Isoxazole, benzisothiazole, benzimidazole, pyridine, pyridine, pyridine, pyrimidine, tris, quinoline, isoquinoline, quinoline, quinoline oxoline ring, phenanthrene ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

As a substituent which a divalent aromatic ring group 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. Among these, from the viewpoint of sclerosing properties, unsubstituted is preferable.

Moreover, as a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and one or more can be mentioned. A group formed by linking the above-mentioned divalent aromatic ring groups. 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, sclerosis|hardenability tends to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as said upper limit or less.

As a specific example of the group which couple|bonded one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the group etc. which are represented by following formula (i-A) - (i-E) are mentioned. Among these, from the viewpoint of developing solubility, a group represented by the following formula (i-A) is preferable. * in the chemical formula represents a bond.

[Chemical 22]

As mentioned above, the benzene ring in formula (i) may be further substituted with any substituent. As this substituent, 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. Among these, from the viewpoint of sclerosing properties, unsubstituted is preferable.

In addition, the partial structure represented by the general formula (i) above is preferably a partial structure represented by the following general formula (i-1) from the viewpoint of curability.

[Chemical 23]

In the formula (i-1), R ^a and R ^b have the same meanings as those in the above-mentioned formula (i), R ^X represents a hydrogen atom or a polybasic acid residue, and ﹡ represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

The polybasic acid residue means a valent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. , one of benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloro bridge acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid or two or more. Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itonic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid are preferred as the polybasic acid. Dicarboxylic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, and biphenyltetracarboxylic acid.

The partial structure represented by the above formula (i-1) contained in the molecule of the epoxy (meth)acrylate resin (b1-B) 1 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.

In addition, the number of the partial structures represented by the above formula (i) contained in one molecule of the epoxy (meth)acrylate resin (b1-B) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for sclerosis|hardenability to become favorable, and it exists in the tendency for image development solubility to become favorable by setting it as the said upper limit or less.

Specific examples of the epoxy (meth)acrylate-based 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. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

The number of rings possessed by the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Moreover, the carbon number 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, further preferably 20 or less, particularly preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norane ring, an isoxane ring, and adamantane. Ring etc. Among these, from the viewpoint of reliability, an adamantane ring is preferred.

環、聯三伸苯環、苊環、螢蒽環、茀環等。該等中，就圖案化特性之觀點而言，較佳為茀環。On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, more preferably 4 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. Moreover, 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, particularly preferably 12 or more, and more preferably 40 or less, more preferably 30 or less, more preferably 20 or less, particularly preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,

Ring, bi-triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring, etc. Among these, from the viewpoint of patterning characteristics, a pylon is preferred.

In addition, 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 and A group formed by linking one or more divalent aromatic ring groups.

The divalent aliphatic group includes linear, branched, cyclic, and a combination of these. Among these, from the viewpoint of compatibility, linear ones are preferable, and on the other hand, from the viewpoint of reliability, cyclic ones are preferable. The number of carbon atoms 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 still more preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

Specific examples of the divalent straight-chain aliphatic group include a methylene group, an ethylidene group, an n-propylidene group, a n-butylene group, a n-hexyl group, and a n-heptide group. Among these, a methylene group is preferable from a sclerosing viewpoint. Specific examples of the divalent branched-chain aliphatic group include the above-mentioned divalent straight-chain aliphatic groups having methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, 2-butyl, 3-butyl, etc. are used as the structure of the side chain. The number of rings that the divalent cyclic aliphatic group has 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norxane ring, an isoxane ring, and an adamantane ring. A base formed by removing 2 hydrogen atoms from a ring such as this. Among these, from the viewpoint of reliability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.

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; a carboxyl group, and the like. Among them, unsubstituted is preferable from the viewpoint of ease of synthesis.

Moreover, as a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and more preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

環、聯三伸苯環、苊環、螢蒽環、茀環等基。 又，作為芳香族雜環基中之雜芳香環，可為單環，亦可為縮合環。作為二價芳香族雜環基，例如可列舉具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等基。 二價芳香族環基中，就圖案化特性之觀點而言，較佳為具有2個自由原子價之苯環、具有2個自由原子價之萘環、或具有2個自由原子價之茀環，更佳為具有2個自由原子價之茀環。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 having two free valences, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,

ring, bi-triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring and other bases. In addition, 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 having two free valences, 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, furopyrrole ring, furofuran ring, thienofuran ring, benzene Isoxazole, benzisothiazole, benzimidazole, pyridine, pyridine, pyridine, pyrimidine, tris, quinoline, isoquinoline, quinoline, quinoline oxoline ring, phenanthrene ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Among the divalent aromatic ring groups, from the viewpoint of patterning properties, a benzene ring having two free valences, a naphthalene ring having two free valences, or a perylene ring having two free valences is preferred , more preferably a perylene ring with 2 free valences.

As a substituent which a divalent aromatic ring group 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. Among these, from the viewpoint of developing solubility and moisture absorption resistance, unsubstituted is preferable.

Moreover, as a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and one or more can be mentioned. A group formed by linking the above-mentioned divalent aromatic ring groups. 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less.

As a specific example of the group which couple|bonded one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the group etc. which are represented by said formula (i-A) - (i-E) are mentioned. Among these, the group represented by the above formula (i-C) is preferable from the viewpoint of reliability.

The cyclic hydrocarbon as the side chain is not particularly limited based on the bonding form of the divalent hydrocarbon group, for example, a form in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain is exemplified , or an aspect in which a cyclic hydrocarbon group as a side chain is formed including one carbon atom of an aliphatic group.

In addition, the partial structure represented by the above 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 the above formula (ii), R ^α represents a valent cyclic hydrocarbon group which may have a substituent, n is an integer of 1 or more, and * represents a bond. The benzene ring in formula (ii-1) may be further substituted with any substituent.

(R ^α ) In the above formula (ii-1), R ^α represents a valent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

The number of rings possessed by the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Moreover, the carbon number 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, further preferably 20 or less, particularly preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norane ring, an isoxane ring, and adamantane. Ring etc. Among these, from the viewpoint of compatibility, an adamantane ring is preferred.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. Moreover, the carbon number of an aromatic ring group is 4 or more normally, Preferably it is 5 or more, More preferably, it is 6 or more, Furthermore, it is preferable that it is 30 or less, More preferably, it is 20 or less, More preferably, it is 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. As a specific example of the aromatic ring in an aromatic ring group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, etc. are mentioned. Of these, from the viewpoint of reliability, a chimney is preferable.

Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and the like. Alkyl groups with 1 to 5 carbon atoms; alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; nitro groups; cyano groups; carboxyl groups and the like. Of these, from the viewpoint of ease of synthesis, unsubstituted is preferred.

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

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

As described above, the benzene ring in formula (ii-1) may be further substituted with any substituent. As this substituent, 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. Of these, from the viewpoint of patterning properties, it is preferably unsubstituted.

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

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

In addition, the partial structure represented by the above-mentioned general formula (ii) is preferably a partial structure represented by the following general formula (ii-2) from the viewpoint of reliability.

[Chemical 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 bond. The benzene ring in formula (ii-2) may be further substituted with any substituent.

(R ^β ) In the above formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

The number of rings possessed by the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Moreover, the carbon number 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 35 or less, and still more preferably 30 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norane ring, an isoxane ring, and adamantane. Ring etc. Among these, from the viewpoint of compatibility, an adamantane ring is preferred.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, more preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to become favorable, and it exists in the tendency for sclerosis|hardenability to become favorable by setting it as the said upper limit or less. As a specific example of the aromatic ring in an aromatic ring group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, etc. are mentioned. Of these, from the viewpoint of reliability, a chimney is preferable.

Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and the like. Alkyl groups with 1 to 5 carbon atoms; alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; nitro groups; cyano groups; carboxyl groups and the like. Of these, unsubstituted is preferred from the viewpoint of ease of synthesis.

Among these, from the viewpoint of compatibility, R ^β is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group. On the other hand, from the viewpoint of reliability, R ^β is preferably a divalent aromatic ring group, more preferably a divalent perylene ring group.

As mentioned above, the benzene ring in formula (ii-2) may be further substituted with any substituent. As this substituent, 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. Moreover, two benzene rings in formula (ii-2) may be connected via these substituents. Of these, from the viewpoint of patterning properties, it is preferably unsubstituted.

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

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

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

[Chemical 39]

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

The polybasic acid residue means a valent group obtained by removing one OH group from a polybasic acid or its anhydride. Furthermore, one OH group can be further removed and shared with R ^Z in other molecules represented by formula (ii-3), that is, a plurality of formula (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, and trimellitic acid. , one of benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloro bridge acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid or two or more. Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itonic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid are preferred as the polybasic acid. Dicarboxylic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, and biphenyltetracarboxylic acid.

The partial structure represented by the above formula (ii-3) contained in the epoxy (meth)acrylate resin (b1-C) 1 molecule 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 polyacid residue.

In addition, the number of the partial structures represented by the above formula (II) contained in one molecule of the epoxy (meth)acrylate resin (b1-C) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for sclerosis|hardenability to become favorable, and it exists in the tendency for image development solubility to become favorable by setting it as the said upper limit or less.

The epoxy (meth)acrylate resin (b1) may be used alone or in combination of two or more. Moreover, a part of the epoxy (meth)acrylate resin (b1) mentioned above can be substituted with another binder resin and can be used. That is, epoxy (meth)acrylate resin (b1) can be used together 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% by mass or more, more preferably 10% by mass or more, and further It is preferably 20 mass % or more, more preferably 30 mass % or more, particularly preferably 40 mass % or more, and most preferably 50 mass % or more. Moreover, it is preferable to set it as 90 mass % or less, It is more preferable to set it as 80 mass % or less, It is still more preferable to set it as 70 mass % or less, It is especially preferable to set it as 60 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, still more preferably 30 to 70% by mass, particularly preferably 40 to 60% by mass, and most preferably 50 to 60% by mass quality%.

The other binder resin which can be used together with the epoxy (meth)acrylate resin (b1) is not limited, and may be selected from resins generally used for photosensitive coloring compositions. For example, the binder resin etc. which are described in Unexamined-Japanese-Patent No. 2007-271727, Unexamined-Japanese-Patent No. 2007-316620, Unexamined-Japanese-Patent No. 2007-334290, etc. are mentioned. Moreover, from the viewpoint of reliability or surface smoothness, the (meth)acrylic copolymer resin described in International Publication No. 2017/110893 can be preferably used. Furthermore, other binder resins may be used alone or in combination of two or more.

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

Examples of acrylic resins include ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "unsaturated monomers (b2-1)") and other copolymerizable ethylenically unsaturated monomers ( Hereinafter, it is referred to as a copolymer of "unsaturated monomer (b2-2)"). Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic 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 fumaric acid) ) Mono[(meth)acryloyloxyalkanes of polycarboxylic acids with more than two valences, such as acryloyloxyethyl]ester, mono[2-(meth)acryloyloxyethyl]phthalate, etc. [methyl] ester; ω-carboxy polycaprolactone mono (meth) acrylate is equal to the mono (meth) acrylate of a polymer with carboxyl and hydroxyl groups at both ends; p-vinyl benzoic acid, etc. These unsaturated monomers (b2-1) may be used alone, or two or more of them may be used in combination.

Moreover, as an unsaturated monomer (b2-2), N-position substituted maleimide, such as N-phenylmaleimide, N-cyclohexylmaleimide, etc., is mentioned, for example Imine; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene and other aromatic vinyl compounds;

Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, ( Benzyl meth)acrylate, polyethylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polyethylene glycol ( Polymerization degree 2~10) Mono(meth)acrylate, Polypropylene glycol (Polymerization degree 2~10) Mono(meth)acrylate, Cyclohexyl (meth)acrylate, Iso(meth)acrylate, Tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-(meth)acrylate Hydroxyphenyl ester, ethylene oxide modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3 (Meth)acrylates such as [(meth)acrylooxymethyl]oxetane, 3-[(meth)acrylooxymethyl]-3-ethyloxetane, etc. ;

Cyclohexyl vinyl ether, iso(vinyl vinyl ether), tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3 -Vinyl ethers such as ethyl oxetane; polystyrene, polymethyl (meth)acrylate, poly(n-butyl) (meth)acrylate, polysiloxane are equal to the end of the polymer molecular chain with mono(methyl) Base) Acryloyl giant monomer and so on. These unsaturated monomers (b2-2) may be used alone, or two or more of them 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, More preferably, it is 10 to 40 mass %. By copolymerizing the unsaturated monomer (b2-1) within such a range, there is a tendency that a photosensitive coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, 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, Japanese Patent Laid-Open No. 2018-9132, and the like. The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method, for example, Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006 The method disclosed in -259680 Gazette, International Publication No. 2007/029871, etc. controls its structure or Mw, Mw/Mn.

<(c) Photopolymerization initiator> (c) The photopolymerization initiator is a component having the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. Additives, such as a polymerization accelerator (chain transfer agent) and a sensitizing dye, can also be added and used as needed. Examples of photopolymerization initiators 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 No. 56118; -N-aryl-α-amino acids such as phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other radical activators, α -Amino 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)bisphenyl titanium, 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, etc.

Moreover, as biimidazole derivatives, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5- Bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl) )-4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc.

Moreover, as halomethylated oxadiazole derivatives, 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl Methyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6' '-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc.

In addition, examples of halomethyl-messium-trisium derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)meses-trissium, 2-(4-methoxyphenyl)- Naphthyl)-4,6-bis(trichloromethyl)stris, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)stris, 2-( 4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)stris, etc.

Moreover, as α-aminoalkylphenone derivatives, 2-methyl-1[4-(methylthio)phenyl]-2-𠰌olinopropan-1-one, 2-benzyl Alkyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)butanone Alkan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 1, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethyl) Aminobenzyl)coumarin, 4-(diethylamino)chalcone, etc.

As a photopolymerization initiator, an oxime ester compound is effective especially in terms of sensitivity and plate-making properties, but when an alkali-soluble resin containing a phenolic hydroxyl group is used, it becomes Since it is unfavorable, especially such an oxime ester compound which is excellent in sensitivity is useful. Since the oxime ester compound has both the structure of absorbing ultraviolet rays, the structure of transmitting light energy and the structure of generating free radicals in its structure, the sensitivity is high in a small amount, and it is relatively stable in terms of thermal reaction, and a small amount of high sensitivity can be obtained. Photosensitive coloring composition.

As an oxime ester type compound, the compound represented by following general formula (IV) is mentioned, for example.

[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 an arbitrary substituent including an aromatic ring, and R ^22a represents a substituent which may have a substituent The alkane group or the aryl group which may have a substituent, n represents an integer of 0 or 1.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, a propyl group, and the like. 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 amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2 -Methylphenyl, N-acetyl-N-acetyloxyamino, etc., 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. Although the carbon number of an aromatic ring group is not specifically limited, From a viewpoint of solubility in a photosensitive coloring composition, 5 or more are preferable. Moreover, from the viewpoint of developability, 30 or less are preferable, 20 or less are more preferable, and 12 or less are still more preferable.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furanyl group, and the like. Among these, a phenyl group or a naphthyl group is preferred, and a benzene group is more preferred from the viewpoint of developability. base. Examples of the substituent which the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, a group in which these substituents are linked, and the like. From a viewpoint, an alkyl group, an alkoxy group, and a group formed by connecting these are preferable, and an alkoxy group formed by connection 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 which has an alkoxy group connected to the substituent.

基或可經取代之二苯硫醚基。該等中，就感度之觀點而言，較佳為可經取代之咔唑基。Moreover, as R< ^21b >, the carbazolyl group which may be substituted, the 9-oxosulfan which may be substituted are preferably mentioned

group or a diphenyl sulfide group which may be substituted. Among these, from the viewpoint of sensitivity, a substituted carbazolyl group is preferred.

In addition, the carbon number of the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably Preferably it is 15 or less, More preferably, it is 10 or less, More preferably, it is 5 or less. As a specific example of an alkanoyl group, an acetyl group, a propionyl group, a butyryl group, etc. are mentioned. Examples of the substituent which the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and the like, and it is preferably unsubstituted from the viewpoint of ease of synthesis.

In addition, the carbon number of the aryl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably Preferably it is 15 or less, More preferably, it is 10 or less. Specific examples of the aryl group include a benzyl group, a naphthyl group, and the like. Examples of the substituent that the aryl aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and the like, and it is preferably unsubstituted from the viewpoint of ease of synthesis. Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and still more preferably an acetyl group.

Moreover, the initiator described in Japanese Patent Laid-Open No. 2016-133574 can also be suitably used from the viewpoint of reducing the contamination of the liquid crystal layer by the colorant.

色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報所記載之具有雜環之香豆素色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報所記載之3-酮香豆素化合物；日本專利特開平6-19240號公報所記載之吡咯亞甲基色素；以及日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本專利特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報所記載之具有二烷基胺基苯骨架之色素等。The photopolymerization initiator may be used alone or in combination of two or more. If necessary, for the purpose of increasing the sensitivity, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source are prepared in the photopolymerization initiator. Examples of sensitizing dyes include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. Hei 4-219756.

Pigment; Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, Coumarin pigments with heterocycles; Japanese Patent Laid-open No. 3-239703, Japanese Patent Laid-open No. 5-289335 The 3-ketocoumarin compound described in the publication No. ; the pyrrolomethylene dye described in the Japanese Patent Laid-Open No. 6-19240; Japanese Patent Laid-Open No. 155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-15503, Japanese Patent Laid-Open No. 58-15503 Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, The dye and the like having a dialkylaminobenzene skeleton are described in Japanese Patent Laid-Open No. 5-210240 and Japanese Patent Laid-Open No. 4-288818.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the molecule. Particularly preferred ones 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]benzoxazole 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-diethylaminophenyl) Aminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylamine) (p-dimethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl) Pyrimidine and other compounds containing p-dialkylamino phenyl, etc. Among them, the best one is 4,4'-dialkylaminobenzophenone. One of the sensitizing dyes may be used alone, or two or more of them may be used in combination.

As the polymerization accelerator, for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate can be used; aliphatic amines such as n-butylamine and N-methyldiethanolamine; the following The mercapto compounds, etc. A polymerization accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

<(d) ethylenically unsaturated compound> The photosensitive coloring composition of this invention contains (d) an ethylenically unsaturated compound. The sensitivity is improved by containing the (d) ethylenically unsaturated compound. The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, and a monoester of a carboxylic acid having one ethylenically unsaturated bond and a polyvalent or monovalent alcohol, etc. .

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 contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less , more preferably 7 or less. By setting it as the said lower limit or more, there exists a tendency for high sensitivity, and by setting it as the said upper limit or less, solubility in a solvent tends to improve. As a combination of an upper limit and a lower limit, 2-8 are preferable, for example, 4-8 are more preferable, and 5-7 are still more preferable. Examples of polyfunctional vinyl monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Polyvalent hydroxy compounds such as polyhydroxy compounds, unsaturated carboxylic acids and esters obtained by esterification of polyvalent carboxylic acids, etc.

As the ester of the said aliphatic polyhydroxy compound and unsaturated carboxylic acid, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate are mentioned. Acrylates of aliphatic polyhydroxy compounds such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. The acrylate of the exemplified compound is replaced by the methacrylate of the methacrylate, similarly by the itonate of the itonate, by the crotonate by the crotonate, or by the maleate Maleic acid esters, etc.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol dimethyl Acrylates and methacrylates of aromatic polyhydroxy compounds such as acrylates and pyrogallol triacrylates.

The ester obtained by the esterification reaction of a polyvalent carboxylic acid, an unsaturated carboxylic acid, and a polyvalent hydroxy compound is not necessarily a single substance, but representative specific examples include 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, butylene glycol and glycerin condensate, etc.

In addition, as an example of the polyfunctional vinylic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate or a polyisocyanate compound and a polyol and a hydroxyl group-containing compound are useful. (meth)acrylate urethanes obtained by the reaction of (meth)acrylates; such as epoxy acrylic acid of the addition reaction product of polyvalent epoxy compound and hydroxy (meth)acrylate or (meth)acrylic acid Esters; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate, etc.

Examples of the above-mentioned (meth)acrylate 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 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd. ), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), etc.

Among these, as the (d) ethylenically unsaturated compound, alkyl (meth)acrylate is preferably used, and dipentaerythritol hexaacrylate is more preferably used from the viewpoint of curability. These may be used individually by 1 type, and may use 2 or more types together.

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

Among the organic solvents, from the viewpoint of coatability, it is preferable to select a boiling point within a range of 100 to 300°C, and more preferably a boiling point within a range of 120 to 280°C. Furthermore, the boiling point referred to here means the boiling point at a pressure of 1013.25 hPa, and the same applies to the boiling point below.

As such an organic solvent, the following are mentioned, for example. 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 tertiary butyl ether, diethyl ether Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl amyl alcohol, 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, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethyl glycol Glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether kind;

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 Acetate, Propylene Glycol Monobutyl Ether Acetate, Butyl Methoxyacetate, Butyl 3-Methoxyacetate, Amyl Methoxyacetate, Diethylene Glycol Monomethyl Ether Acetate, Diethylene Glycol Monoacetate 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 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; Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether 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 , ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentyl ketone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexane Monohydric or polyhydric alcohols such as alcohol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentanol, 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; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylenediol Alcohol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethyl acetate Methyl oxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, 3-methylpropionate Chain or cyclic esters such as butyl oxypropionate, gamma-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; chlorobutane , halogenated hydrocarbons such as chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile, etc.

Examples of commercially available organic solvents equivalent to the above include: Mineral spirits, Varsol #2, Apco #18 solvent, Apco thinner, Socal solvent No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, card Biol, ethyl carbitol, butyl carbitol, methyl celsulu ("Salusu" is a registered trademark; the same below), ethyl cilusu, ethyl cilusu acetate, methyl cilusu Kisellus Acetate, Diethylene Glycol Dimethyl Ether (all trade names), etc. These organic solvents may be used alone or in combination of two or more.

In the case of forming the colored spacer by photolithography, it is preferable to select the range of the boiling point of 100-200 degreeC as an organic solvent. More preferably, it has a boiling point of 120-170 degreeC.

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferable in that the balance of coatability, surface tension, etc. is good, and the solubility of the constituent components in the composition is relatively high. In addition, the glycol alkyl ether acetates may be used alone, or other organic solvents may be used in combination. As the organic solvent to be used together, glycol monoalkyl ethers are particularly preferred. Among them, propylene glycol monomethyl ether is preferable in view of the solubility of the constituents in the composition in particular. Furthermore, glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate easily, and the viscosity of the photosensitive coloring composition obtained thereafter tends to decrease in storage stability. The ratio of glycol monoalkyl ethers is preferably 5 to 30 mass %, more preferably 5 to 20 mass %.

Moreover, it is also preferable to use together the organic solvent which has a boiling point of 150 degreeC or more (Hereinafter, it may be called "high-boiling-point solvent"). By using such a high boiling point solvent together, the photosensitive coloring composition becomes difficult to dry, and there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, there is an effect of preventing the occurrence of impurity defects caused by precipitation and curing of colorants at the tip of the slit nozzle, for example. In terms of the 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 preferable.

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% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, particularly preferably 5% by mass to 30% by mass %. By setting the above lower limit value or more, for example, the precipitation and curing of colorants at the tip of the slit nozzle and the like tend to be suppressed to cause impurity defects, and by setting the above upper limit value or less, the combination can be suppressed. The drying temperature of the material is slowed down, and the tendency of problems such as poor touch in the vacuum drying process or stomata marks in the pre-baking process is suppressed.

Furthermore, the high-boiling point solvent with a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, it is not necessary to additionally contain a high-boiling point solvent with a boiling point of 150°C or higher. . As a preferable high boiling point solvent, for example, among the various solvents mentioned above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1 , 3-Butanediol diacetate, 1,6-hexanol diacetate, triacetin, etc.

<(f) Dispersing agent> In the photosensitive coloring composition of this invention, (f) dispersing agent may be contained for the purpose of finely dispersing the (a) coloring agent and stabilizing the dispersion state. As the dispersant (f), a polymer dispersant having a functional group is preferred, and from the viewpoint of dispersion stability, a polymer dispersant having functional groups such as the following groups is preferred: carboxyl group; phosphoric acid group; sulfonic acid group Acid group; or the group of these salts; primary, secondary or tertiary amine group; quaternary ammonium salt group; group derived from pyridine, pyrimidine, pyridine and other nitrogen-containing heterocycles. Among them, especially from the viewpoint of dispersing with a small amount of dispersing agent when dispersing pigments, polymer dispersing agents having basic functional groups such as the following groups are particularly preferred: primary, secondary or tertiary amine groups; quaternary ammonium groups Base; bases derived from pyridine, pyrimidine, pyridine and other nitrogen-containing heterocycles.

Moreover, as a polymer dispersant, for example, a urethane-based dispersant, an acrylic-based dispersant, a polyethylenimine-based dispersant, a polyallylamine-based dispersant, a Monomer and macromonomer dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic esters dispersant, aliphatic modified polyester dispersant, etc.

Specific examples of such dispersants include the following trade names: EFKA (registered trademark; manufactured by BASF Corporation), DISPERBYK (registered trademark; manufactured by BYK-Chemie Corporation), Disparlon (registered trademark; manufactured by Kusumoto Chemical Corporation), SOLSPERSE (registered trademark; manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyōeisha Chemical Corporation), Ajisper (registered trademark; manufactured by Ajinomoto Corporation), and the like. These polymer dispersants may be used alone, or two or more of them may be used in combination.

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

Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK160 to 166, 182 series (all of which are urethane-based), DISPERBYK2000, 2001, BYK-LPN21116, etc. (all of which are acrylic-based) (All of the above are manufactured by BYK-Chemie Corporation). As a urethane-based polymer dispersant, if a preferable chemical structure is specifically exemplified, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, And the dispersion resin with weight average molecular weight of 1,000-200,000 obtained by reacting the compound with active hydrogen and tertiary amine group in the molecule. By treating these with a quaternary agent such as benzyl chloride, all or part of the tertiary amine groups can be turned into quaternary ammonium salt groups.

Examples of the above-mentioned polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5- Aromatic diisocyanates such as diisocyanate and bitoluidine diisocyanate; hexamethylene diisocyanate, methyl lysine diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Aliphatic diisocyanates such as isophorone diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), ω,ω'-diisocyanatodimethylcyclohexane; Aliphatic diisocyanates with aromatic rings such as xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate; lysine triisocyanate, 1,6,11-deca Monoalkane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanato) triisocyanates such as acid phenyl) methane, tris(isocyanatophenyl) phosphorothioate; and these trimers, water adducts, and these polyol adducts, etc. As the polyisocyanate, a trimer of organic diisocyanate is preferable, and a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate are most preferable. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanates, there may be mentioned a method in which the above-mentioned trimerization catalysts, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., are used as appropriate trimerization catalysts to make the above Polyisocyanates undergo partial trimerization of isocyanate groups. After the trimerization is stopped by adding catalyst poison, the unreacted polyisocyanates are removed by solvent extraction and thin film distillation to obtain the target isocyanurate-containing esters. based polyisocyanates.

As a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin diol can be exemplified. Alcohols, etc., as well as compounds obtained by alkoxylation of a single terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these compounds. As a polyether glycol (polyether glycol), a polyether diol (polyether diol), a polyether ester diol (polyetherester diol), and the mixture of these two or more types are mentioned. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxide, and examples thereof include polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, and polyoxytetramethylene. base glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more of these.

Examples of the polyetherester diol include reacting an ether group-containing diol or a mixture thereof with other diols with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester diol (polyester diol). Glycol) and an alkylene oxide are obtained by reacting, for example, poly (polyoxytetramethylene) adipate etc. are mentioned. As the polyether glycol, the most preferable one is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or the compound of these. The single terminal hydroxyl group is alkoxylated by an alkyl group having 1 to 25 carbon atoms. base compounds.

As polyester glycol, dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid) can be mentioned. 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 yl-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 benzenedimethanol and bishydroxyethoxybenzene; N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.) obtained by polycondensation, such as poly Ethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene adipate/propylene adipate, etc.; ) or monohydric alcohols with 1 to 25 carbon atoms as initiators to obtain polylactone diols or polylactone monools, such as polycaprolactone diol, polymethylvalerolactone and two of these a mixture of the above. As the polyester glycol, polycaprolactone glycol or polycaprolactone having an alcohol having 1 to 25 carbon atoms as an initiator is most preferable.

Polycarbonate (1,6-hexanediol), polycarbonate (3-methyl-1,5-pentanediol), etc. are mentioned as polycarbonate diol, and polybutanediol is mentioned as polyolefin diol alkene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, etc. These may be used individually by 1 type, and may use 2 or more types together.

The number average molecular weight of the compound having one or two hydroxyl groups in the molecule is usually 300 to 10000, preferably 500 to 6000, and more preferably 1000 to 4000.

The compound having an active hydrogen and a tertiary amine group in the molecule used in the present invention will be described. Examples of active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom, include hydrogen atoms in functional groups such as a hydroxyl group, an amine group, and a thiol group. The hydrogen atom of the amine group.

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, and more specifically, an imidazole ring, a triazole ring, and the like are mentioned. 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-propanediamine 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-diamine Ethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc.

In addition, as the nitrogen-containing heterocyclic ring when the tertiary amino group is a nitrogen-containing heterocyclic ring structure, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indole ring can be mentioned. azole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring and other nitrogen-containing five-membered heterocycles; pyridine ring, pyridine ring, pyrimidine ring, three 𠯤 ring, quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing six-membered heterocycles. Among these nitrogen-containing heterocycles, 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 etc. Moreover, if the compound which has a triazole ring and an amine 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, etc. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3 -amino-1,2,4-triazole. These may be used individually by 1 type, and may use 2 or more types together.

The preferable mixing ratio of the raw materials for the production of the urethane polymer dispersant is 10 to 200 of the compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule relative to 100 parts by mass of the polyisocyanate compound. The mass part is preferably 20-190 mass parts, more preferably 30-180 mass parts, and the compound having active hydrogen and tertiary amine group in the molecule is 0.2-25 mass parts, preferably 0.3-24 mass parts.

The production of the urethane-based polymer dispersant is carried out in accordance with a known method for producing a polyurethane resin. As a solvent for production, generally used: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; ethyl acetate, butyl acetate, acetonitrile Esters such as Lusu; Hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, second butanol, and third butanol; chlorides such as dichloromethane and chloroform; Ethers such as tetrahydrofuran and diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc. These may be used individually by 1 type, and may use 2 or more types together.

In the above-mentioned production, a urethane-forming reaction catalyst is usually used. Examples of the catalyst include: tin-based such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; series; tertiary amine series such as triethylamine, triethylenediamine, etc. These may be used individually by 1 type, and may use 2 or more types together.

The introduction amount of the compound having active hydrogen and tertiary amine group in the molecule is preferably controlled in the range of 1-100 mgKOH/g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value by titrating basic amine groups by acid neutralization. By setting it as the said lower limit or more, there exists a tendency for a dispersibility to become favorable, and it exists in the tendency which becomes easy to suppress the fall of developability by setting it as the said upper limit or less.

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 over time of the product becomes high, 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. By making it more than the said lower limit, there exists a tendency for dispersibility and dispersion stability to become favorable, and there exists a tendency for the fall of solubility or dispersibility to be suppressed easily by making it less than the said upper limit.

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

Specific examples of the unsaturated group-containing monomer having a functional group include the following: (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-((meth)phthalate) Unsaturated monomers with carboxyl groups such as meth)acryloyloxyethyl ester, 2-(meth)acryloyloxyethyl hexahydrophthalate, and acrylic acid dimer; (meth)acrylic acid dimethylamine Unsaturated monomers with tertiary amine group and quaternary ammonium salt group, such as ethyl ethyl ester, diethylaminoethyl (meth)acrylate, and quaternary products of these. These may be used individually by 1 type, and may use 2 or more types together.

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, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, ring (meth)acrylate Hexyl ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, iso(meth)acrylate, (meth)acrylate ) Tricyclodecyl acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene; N-cyclohexylmaleimide , N-substituted maleimide such as N-phenylmaleimide, N-benzylmaleimide, etc.; acrylonitrile, vinyl acetate and poly(meth)acrylate Ester macromonomer, polystyrene macromonomer, poly(meth)acrylate 2-hydroxyethyl ester macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer and other macromonomers Monomer, etc. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer comprising an A block having a functional group and a B block having no functional group. In addition to the partial structure of the functional group-containing unsaturated group-containing monomer, it may also contain a partial structure derived from the above-mentioned non-functional group-containing unsaturated group-containing monomer, which can be randomly copolymerized or block copolymerized Either aspect is contained in the A block. Moreover, the content rate of the partial structure which does not contain a functional group in A block is 80 mass % or less normally, Preferably it is 50 mass % or less, More preferably, it is 30 mass % or less.

The B block contains a partial structure derived from the above-mentioned unsaturated group-containing monomer without a functional group, and one B block may also contain two or more partial structures derived from the monomer. Either a regular copolymerization or a block copolymerization is contained in the B block. The A-B or B-A-B block copolymer is prepared, for example, by the living polymerization method shown below. Living polymerization methods include anionic living polymerization, cationic living polymerization, and radical living polymerization, wherein the polymerization active species of anionic living polymerization is anion, for example, it is represented by the following process.

[Chemical 41]

In the above process, 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 it is represented by the following scheme, for example.

[Chemical 42]

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

When synthesizing the acrylic polymer dispersant, Japanese Patent Laid-Open No. 9-62002, or P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B.C. Anderson, G.D. Andrews can be used et al, Macromolecules, 14, 1601(1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977(1985), 18, 1037(1986), Koichi Right, Koichi Hatada, Polymer Processing , 36, 366(1987), Tominobu Higashimura, Mitsuo Sawamoto, Proceedings of Polymer, 46, 189(1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737(1987), A known method described in Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.Y. Sogoh, W.R. Hertler et al, Macromolecules, 20, 1473 (1987).

The acrylic polymer dispersant that can be used in the present invention can be A-B block copolymer or B-A-B block copolymer, and the ratio of A block/B block constituting the copolymer is preferably 1/99～80/20 , 5/95 to 60/40 (mass ratio) is particularly preferable, and by setting it within this range, the balance between dispersibility and storage stability tends to be secured. In addition, the amount of the A-B block copolymer and the quaternary ammonium salt group in 1 g of the B-A-B block copolymer that can be used in the present invention is generally preferably 0.1 to 10 mmol, and by setting it within this range, it is possible to ensure good The tendency of dispersion.

In addition, such block copolymers usually contain amine groups generated during the production process, and the amine value is about 1 to 100 mgKOH/g, preferably 10 from the viewpoint of dispersibility. mgKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, and more preferably 75 mgKOH/g /g or less. The combination of the upper limit and the lower limit is, for example, preferably 10 to 90 mgKOH/g, more preferably 30 to 80 mgKOH/g, and still more preferably 50 to 75 mgKOH/g. Here, the amine value of dispersing agents such as these block copolymers is expressed by the mass of KOH equivalent to the base equivalent per 1 g of the solid content other than the solvent in the dispersing agent sample, and is determined by the following method. Determination. Accurately weigh 0.5-1.5 g of dispersant sample into a 100 mL beaker, and dissolve it with 50 mL of acetic acid. The solution was neutralized and titrated with a 0.1 mol/L HClO ₄ acetic acid solution using an automatic titration device equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of the titration, the amine value was obtained by the following formula.

Amine value [mgKOH/g]=(561×V)/(W×S) [wherein, W represents the weighed amount of the dispersant sample [g], V represents the titration amount at the end of the titration [mL], and S represents the dispersant The solid content concentration of the sample [mass %]] In addition, the acid value of the block copolymer also depends on the presence and type of the acid group that is the source of the acid value. Generally, a lower value is appropriate, usually 10 mgKOH/ g or less, the weight average molecular weight (Mw) is preferably in the range of 1,000 to 100,000. By setting it in 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, but from the viewpoint of dispersibility, it is preferable to have the following The repeating unit represented by the 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 that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent, and among R ³¹ to R ³³ Two or more of them can be bonded to each other to form a cyclic structure, R ³⁴ is a hydrogen atom or a methyl group, X is a divalent linking group, and Y ^- is a counter anion.

The carbon number of the optionally substituted alkyl group in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like, among these, a methyl group, an ethyl group, a propyl group, a Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, any of a linear form and a branched form may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be contained.

The carbon number of the optionally substituted aryl group in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group, and the like, and among these, benzene is preferred phenyl, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

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

Moreover, when the acrylic polymer dispersant has a tertiary amino group as a functional group, it is preferable to have a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as the following formula) from the viewpoint of dispersibility. "repeating 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, and R ³⁵ and R ³⁶ may be They are 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 in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably used. Likewise, as the optionally substituted aryl group in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably used. Moreover, as the aralkyl group which may have a substituent among R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably used.

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

Examples of substituents that the alkyl group, aralkyl group or aryl group in R ³¹ to R ³³ of the above formula (i) and R ³⁵ and R ³⁶ of the above formula (ii) may have include a halogen atom, an alkoxy group , benzyl, hydroxyl, etc.

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and -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., preferably For -COO-R ⁴⁴ - group. In addition, in the above formula (i), examples of Y ^- of the counter anion 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. From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (i) and the above formula (ii) The total content of the repeating unit is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, particularly preferably 35 mol% or less, and more preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 20 mol% or more, particularly preferably 30 mol% or more.

In addition, the content ratio of the repeating unit represented by the above formula (i) to the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, and more It is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 50 mol% or less, more preferably 30 mol% or less, and then preferably 20 mol% or less, especially 15 mol% or less.

In addition, 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, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, and more Preferably it is more than 10 mol%, more preferably more than 15 mol%, more preferably more than 20 mol%, and more preferably less than 60 mol%, more preferably less than 40 mol%, and then preferably It is 30 mol% or less, more preferably 25 mol% or less.

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

[Chemical 45]

In the above formula (iii), R ⁴⁰ is an ethylidene or propylidene group, R ⁴¹ is an optionally substituted alkyl group, R ⁴² is a hydrogen atom or a methyl group, and n is an integer of 1-20.

The carbon number of the optionally substituted alkyl group in R ⁴¹ of the above formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like, among these, a methyl group, an ethyl group, a propyl group, a Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, any of a linear form and a branched form may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be contained.

In addition, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, more preferably 10 or less, from the viewpoint of compatibility and dispersibility with respect to adhesive components such as a solvent and the like. Preferably it is 5 or less.

In addition, the content ratio of the repeating unit represented by the above formula (iii) in the total repeating unit of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, More preferably, it is 4 mol % or more, and more preferably 30 mol % or less, more preferably 20 mol % or less, and still more preferably 10 mol % or less. When it is the case within the said range, there exists a tendency for compatibility with respect to adhesive components, such as a solvent, and dispersion stability to be compatible.

In addition, the polymer dispersing agent preferably has a repeating unit represented by the following formula (iv) (hereinafter sometimes referred to as the following: is "repeating unit (iv)").

[Chemical 46]

In the above formula (iv), R ³⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and R ³⁹ is a hydrogen atom or a methyl group.

The carbon number of the optionally substituted alkyl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, More preferably, it is 8 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like, among these, a methyl group, an ethyl group, a propyl group, a Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, any of a linear form and a branched form may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be contained.

The carbon number of the optionally substituted aryl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less . Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group, and the like, and among these, benzene is preferred phenyl, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

The carbon number of the optionally substituted aralkyl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, and still more preferably 10 the following. Specific examples of the aralkyl group include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl. Among 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, more preferably a methyl group, an ethyl group, or a phenylmethyl group. As a substituent which the alkyl group in ^R38 may have, a halogen atom, an alkoxy group, etc. are mentioned. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. In addition, the chain-like alkyl group represented by R ³⁸ includes any of straight-chain and branched-chain ones.

In addition, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol % or more, more preferably 40 mol % from the viewpoint of dispersibility % or more, more preferably 50 mol % or more, and more preferably 80 mol % or less, 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; and (meth)acrylate-based (meth)acrylate-based monomers such as (meth)acryloyl chloride Monomers; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Ether; monomers such as N-methacryloyl quinoline.

From the viewpoint of further improving the dispersibility, the polymer dispersing agent preferably contains the A block having the repeating unit (i) and the repeating unit (ii) and the B block not having the repeating unit (i) and the repeating unit (ii). Block copolymers. 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 unexpectedly tends to be remarkably improved. Moreover, it is preferable that the B block has a repeating unit (iii), and it is more preferable that it further has a repeating unit (iv).

The repeating unit (i) and the repeating unit (ii) may be contained in the A block in any aspect 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, and in this case, each repeating unit may have either random copolymerization or block copolymerization. contained in the A block.

In addition, repeating units other than repeating unit (i) and repeating unit (ii) may be contained in the A block, and examples of such repeating units include (meth)acrylate-derived monolayers described above. repeating units, etc. The content of repeating units other than repeating unit (i) and repeating unit (ii) in the A block is preferably 0-50 mol %, more preferably 0-20 mol %, and most preferably in the A block does not contain this repeating unit.

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)acrylate-based monomers such as (meth)acryloyl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylol acrylamide monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; The content ratio of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0-50 mol %, more preferably 0-20 mol %, and most preferably in the B block does not contain this repeating unit.

Moreover, it is preferable to use (f) a dispersing agent together with the pigment derivative mentioned later from the point of improving dispersion stability.

<Other preparation components of the photosensitive coloring composition> In the photosensitive coloring composition of the present invention, in addition to the above-mentioned components, adhesion improvers such as silane coupling agents, surfactants (coatability improvers), and pigments can be appropriately prepared Derivatives, photoacid generators, crosslinking agents, mercapto compounds, development improvers, UV absorbers, antioxidants and other additives.

(1) Adhesion improver In order to improve the adhesiveness with a board|substrate, an adhesion improver may be contained in the photosensitive coloring composition of this invention. As an adhesion improving agent, a silane coupling agent, a phosphoric acid group-containing compound, etc. are preferable. As the kind of the silane coupling agent, one of epoxy-based, (meth)acrylic-based, amino-based, and the like can be used alone, or two or more of them can be mixed and used.

As preferable silane coupling agents, for example, (methyl) Acryloyloxysilanes; 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxysilanes such as bisethoxysilane and 3-glycidoxypropyltriethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; 3-isocyanate group Isocyanatosilanes such as propyltriethoxysilane are particularly preferred as silane coupling agents such as epoxysilanes. The phosphoric acid group-containing compound is preferably a (meth)acryloyl group-containing phosphoric acid ester, and is preferably represented by the following general formula (g1), (g2) or (g3).

[Chemical 47]

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

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

As the surfactant, for example, various ones such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. Among them, nonionic surfactants are preferably used in terms of low possibility of adversely affecting various properties, and among them, fluorine-based or silicon-based surfactants are effective in terms of coating properties. Surfactant. Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 ( Shin-Etsu Silicones), MEGAFAC F-470, MEGAFAC F-475, MEGAFAC F-478, MEGAFAC F-554, MEGAFAC F-559 (DIC), SH7PA (Dow Corning Toray), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M), and the like. In addition, one type of surfactant may be used, or two or more types may be used in combination 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 dispersing aid. Examples of pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, bismuth-based, anthraquinone-based, anion-based Derivatives such as danthrene series, perylene series, perylene series, diketopyrrolopyrrole series, and diketopyrrole series, among them, phthalocyanine series and quinophthalone series are preferred. The substituents of the pigment derivatives include sulfonic acid groups, sulfonamido groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like. A sulfonic acid group is preferred if it is directly or bonded to the pigment skeleton through an alkyl group, an aryl group, a heterocyclic group, or the like. In addition, a plurality of these substituents may be substituted for one pigment skeleton.

Specific examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolo Sulfonic acid derivatives of pyrrole, sulfonic acid derivatives of di㗁𠯤, etc. These may be used individually by 1 type, and may use 2 or more types together.

(4) Photoacid generator The so-called photoacid generator is a compound that can generate an acid by ultraviolet rays. By the action of the acid generated during exposure, a crosslinking agent such as a melamine compound is present, so a crosslinking reaction occurs. . Among the photoacid generators, those having higher solubility in solvents, especially those used in the photosensitive coloring composition, are preferred, for example, diphenyl iodonium, xylyl iodonium, benzene yl(p-anisyl) iodonium, bis(m-nitrophenyl) iodonium, bis(p-tert-butylphenyl) iodonium, bis(p-chlorophenyl) iodonium, bis(n-dodecyl) iodonium, p- Diaryl iodonium such as isobutylphenyl (p-tolyl) iodo, p-isopropylphenyl (p-tolyl) iodo; or triaryl iodonium such as triphenyl iodonium chloride, bromide; or fluoroborate , hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc.; Complexes; or 2-methyl-4,6-bis(trichloromethyl)tris', 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)tris and other three 𠯤 compounds, etc., but not limited to this.

(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. As these crosslinking agents, for example, melamine or guanamine-based compounds represented by the following general formula (6) can be mentioned.

[Chemical 48]

In formula (6), R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ is a -NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ One of R ⁶⁶ and R ⁶⁷ represents -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 group, the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent hydrogen or -CH ₂ OR ⁶⁸ group, 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 group or the 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 as described above, 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 hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, and hexamethoxymethyl melamine , Pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, etc.

[Chemical 49]

In 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 rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ 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, tetramethoxymethylbenzoguanidine Amine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, etc.

Furthermore, the crosslinking agent which has a methylol group or a methylol alkyl ether group can also be used. Examples are listed 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-tris-2-one (commonly known as N-ethyldimethylol-tris-ketone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl Ether form, 3,5-bis(hydroxymethyl)perhydro-1,3,5-bis(hydroxymethyl)-4-one (commonly known as dimethylolurea) or its dimethyl ether form, tetramethylolethyl ether Dialdehyde dialkylurea or its tetramethyl ether.

In addition, these crosslinking agents can be used individually by 1 type, and can also be used in combination of 2 or more types. 0.1-15 mass % is preferable in the total solid content of the photosensitive coloring composition, and, as for the quantity at the time of using a crosslinking agent, 0.5-10 mass % is especially preferable.

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

Examples of the types of mercapto compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, and 1,4-dimethylthiobenzene , Butylene Glycol Dithioglycolate, Butylene Glycol Dithioglycolate, Ethylene Glycol Dithioglycolate, Trimethylolpropane Trithioglycolate, Butylene Glycol Dithioglycolate acid ester, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithioglycolate Propionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutanoyloxy)butane, trimethylol propane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanedi Alcohol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3, 5-Tris𠯤-2,4,6(1H,3H,5H)-trione and other mercapto compounds or aliphatic polyfunctional mercapto compounds having a heterocyclic ring. These may be used alone or in combination of two or more.

<The compounding quantity of the component in the photosensitive coloring composition> In the photosensitive coloring composition of this invention, the content rate of (a) coloring agent in the total solid content of the photosensitive coloring composition is 23 mass % or less. Since the (a) colorant is a component that does not elastically deform, it is considered that the mechanical properties of the coloring spacer obtained become favorable by setting the content ratio to be equal to or less than the above-mentioned upper limit value. In the total solid content of the photosensitive coloring composition, the content ratio of the colorant (a) is not particularly limited as long as it is 23% by mass or less, but is preferably 22% by mass or less, more preferably 20% by mass or less, and further Preferably it is 18 mass % or less, more preferably 16 mass % or less, particularly preferably 15 mass % or less, most preferably 14 mass % or less, and more preferably 1 mass % or more, more preferably 5 mass % or more , more preferably 8 mass % or more, still more preferably 10 mass % or more, particularly preferably 12 mass % or more. By setting the content ratio of the colorant (a) below the above-mentioned upper limit value, there is a tendency that the mechanical properties become good, and sufficient plate-making properties are easily obtained, and the electrical reliability is excellent, and the above-mentioned Above the lower limit value, 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 mass %, more preferably 5 to 20 mass %, more preferably 8 to 18 mass %, still more preferably 10 to 16 mass %, particularly preferably 10 to 15 mass %, preferably 12 to 14 mass %.

The content ratio of the pigment in the photosensitive coloring composition of the present invention is not particularly limited, but is usually 23% by mass or less, preferably 22% by mass or less, more preferably 23% by mass or less in the total solid content of the photosensitive coloring composition. 20 mass % or less, more preferably 18 mass % or less, still more preferably 16 mass % or less, particularly preferably 15 mass % or less, most preferably 14 mass % or less, and more preferably 1 mass % or more, more Preferably it is 5 mass % or more, More preferably, it is 8 mass % or more, More preferably, it is 10 mass % or more, Especially preferably, it is 12 mass % or more. By setting the content ratio of the pigment to be below the above-mentioned upper limit value, there is a tendency that mechanical properties become good, sufficient plate-making characteristics are easily obtained, and electrical reliability is excellent, and by setting the above-mentioned lower limit value or more, there is a tendency that , there is a tendency to obtain sufficient shading properties. The combination of the upper limit and the lower limit is, for example, preferably 1 to 22 mass %, more preferably 5 to 20 mass %, more preferably 8 to 18 mass %, still more preferably 10 to 16 mass %, particularly preferably 10 to 15 mass %, preferably 12 to 14 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 mass % or more, more preferably 5 mass % or more, still more preferably 8 mass % or more, still more preferably It is 10 mass % or more, more preferably 15 mass % or more, and usually 60 mass % or less, more preferably 50 mass % or less, more preferably 45 mass % or less, still more preferably 40 mass % or less, especially Preferably it is 30 mass % or less, Most preferably, it is 20 mass % or less. By setting the above lower limit value or more, sufficient light-shielding properties can be ensured, and the transmittance at wavelengths of 400 to 500 nm tends to be suppressed. By setting the above upper limit value or less, 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 mass %, more preferably 5 to 50 mass %, more preferably 5 to 45 mass %, still more preferably 8 to 40 mass %, particularly preferably 10 to 30 mass % The mass % is preferably 15 to 20 mass %.

From the viewpoint of hue, the photosensitive coloring composition of the first aspect preferably has a low content ratio of the blue pigment and the violet pigment in all solids, preferably 30% by mass or less, more preferably 25% by mass % or less, more preferably 20 mass % or less, still more preferably 15 mass % or less, particularly preferably 10 mass % or less, particularly preferably 5 mass % or less, and most preferably 0 mass %, that is, no content. On the other hand, from the viewpoint of light-shielding properties, a blue pigment and/or a violet pigment may be contained, and in this case, the content ratio of the blue pigment and the violet pigment in the total solid content is preferably 1% by mass above, more preferably 5 mass % or more, more preferably 8 mass % or more, particularly preferably 10 mass % or more, most preferably 15 mass % or more, and more preferably 30 mass % or less, more preferably 25 mass % % or less, more preferably 20 mass % or less. When it is more than the said lower limit, there exists a tendency for sufficient light-shielding property to be obtained, and it exists in the tendency for the hue close to black to be obtained by setting it as the said upper limit or less. The combination of the upper limit and the lower limit is, for example, preferably 1 to 30 mass %, more preferably 5 to 30 mass %, still more preferably 8 to 25 mass %, still more preferably 10 to 20 mass %, particularly preferably 15 mass % ~20% by mass.

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, more preferably 25% by mass or less, from the viewpoint of light-shielding properties. , more preferably 20 mass % or less, still more preferably 15 mass % or less, particularly preferably 10 mass % or less, particularly preferably 5 mass % or less, and most preferably 0 mass %, that is, no content. 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, and in this case, the content ratio of the yellow pigment in all solids is preferably 1 mass % or more, more It is preferably at least 3 mass %, more preferably at least 5 mass %, particularly preferably at least 10 mass %, and most preferably at least 15 mass %. Moreover, 30 mass % or less is preferable, 25 mass % or less is more preferable, and 20 mass % or less is still more preferable. By setting the above lower limit value or more, the transmittance at a wavelength of 400 to 500 nm tends to be suppressed or a color tone close to black can be obtained. A tendency to increase the optical density (OD). The combination of the upper limit and the lower limit is, for example, preferably 1 to 30 mass %, more preferably 3 to 30 mass %, more preferably 5 to 30 mass %, still more preferably 10 to 25 mass %, particularly preferably 15 mass % ~20% by mass.

In the total solid content of the photosensitive coloring composition of the present invention, the content ratio of the (b) alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably Preferably it is 30 mass % or more, more preferably 35 mass % or more, and usually 85 mass % or less, preferably 80 mass % or less, more preferably 70 mass % or less, still more preferably 60 mass % or less, still more Preferably it is 50 mass % or less, More preferably, it is 45 mass % or less. By making the content ratio of (b) alkali-soluble resin more than the said lower limit, there exists a tendency for a mechanical characteristic to become favorable and developability to become favorable. Moreover, by setting it below the said upper limit, it exists in the tendency to maintain a suitable sensitivity, to suppress the melt|dissolution by a developing solution of an exposure part, and to suppress the fall of adhesiveness. The combination of the upper limit and the lower limit is, for example, preferably 5 to 85 mass %, more preferably 10 to 80 mass %, more preferably 20 to 70 mass %, still more preferably 30 to 60 mass %, particularly preferably 35 to 50 mass %, preferably 35 to 45 mass %.

(c) The content ratio of the photopolymerization initiator is usually 0.1 mass % or more, preferably 0.5 mass % or more, more preferably 1 mass % or more, in the total solid of the photosensitive coloring composition of the present invention, and further 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 particularly preferably 5 mass % or less. By making the content ratio of the (c) photopolymerization initiator more than or equal to the above lower limit value, there is a tendency that the decrease in sensitivity can be suppressed. The solubility is reduced, and the tendency of poor development is suppressed. The combination of the upper limit and the lower limit is, for example, preferably 0.1 to 15 mass %, more preferably 0.5 to 10 mass %, more preferably 1 to 8 mass %, still more preferably 2 to 7 mass %, particularly preferably 2 to 5 mass %.

When (c) the photopolymerization initiator and the polymerization accelerator are used together, the content ratio of the polymerization accelerator is preferably 0.05 mass % or more in the total solids of the photosensitive coloring composition of the present invention, In addition, it is usually 10 mass % or less, preferably 5 mass % or less, and the polymerization accelerator is preferably 0.1 to 50 mass parts and 0.1 to 20 mass parts with respect to 100 mass parts of the (c) photopolymerization initiator. ratio used. By making the content ratio of the polymerization accelerator more than or equal to the above lower limit value, it is possible to suppress the decrease in sensitivity to exposure light, and by making the content ratio of the polymerization accelerator less than or equal to the above upper limit value, it is possible to suppress the loss of unexposed parts with respect to the developing solution. Solubility is reduced, and the tendency of developing failure is suppressed. Moreover, when using (c) a photopolymerization initiator and a sensitizing dye together, the content ratio of the sensitizing dye in the total solid content of the photosensitive coloring composition from the viewpoint of sensitivity is usually It is 20 mass % or less, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less.

In the total solid content of the photosensitive coloring composition of the present invention, the content ratio of the (d) ethylenically unsaturated compound is usually 1 mass % or more, preferably 5 mass % or more, more preferably 10 mass % or more, Furthermore, 20 mass % or more is preferable, 30 mass % or more is especially preferable, and it is usually 70 mass % or less, Preferably it is 60 mass % or less, More preferably, it is 50 mass % or less. By setting the content ratio of the (d) ethylenically unsaturated compound to be equal to or higher than the above-mentioned lower limit value, there is a tendency that the appropriate sensitivity is maintained, the dissolution of the exposed portion by the developer solution can be suppressed, and the decrease in adhesiveness can be suppressed, Moreover, by setting it as the said upper limit or less, it exists in the tendency which suppresses that the permeability|transmittance of a developer with respect to an exposure part becomes high, and it becomes easy to obtain a favorable image. 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, still more preferably 20 to 60% by mass, particularly preferably 30 to 50 mass %.

On the other hand, the content ratio of the (b) 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, still more preferably It is 100 parts by mass or more, and is usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and still more preferably 300 parts by mass or less. By setting the above lower limit value or more, there is a tendency to be in a suitable development state without peeling, etc., and by setting it below the above upper limit value, there is a tendency that a suitable dissolution time for the developer can be obtained. . Moreover, as a combination of the upper limit and the lower limit, for example, preferably 50 to 700 parts by mass, more preferably 80 to 500 parts by mass, still more preferably 80 to 400 parts by mass, and still more preferably 100 to 300 parts by mass parts by mass.

Furthermore, the photosensitive coloring composition of the present invention uses the solvent (e), so that the content ratio of the total solid content is usually 5 mass % or more, preferably 10 mass % or more, more preferably 15 mass % % or more and usually 50 mass % or less, preferably 30 mass % or less, and more preferably 25 mass % or less. As a combination of an upper limit and a lower limit, 5-50 mass % is preferable, 10-30 mass % is more preferable, 15-25 mass % is still more preferable.

When the photosensitive coloring composition of the present invention contains (f) a dispersant, in the total solid content of the photosensitive coloring composition, the content ratio of the (f) dispersant is usually 1 mass % or more, preferably 2 mass % or more, and usually 30 mass % or less, preferably 20 mass % or less, more preferably 15 mass % or less, still more preferably 10 mass % or less, particularly preferably 5 mass % or less. By making the content ratio of the dispersant (f) more than or equal to the above lower limit value, sufficient dispersibility tends to be easily obtained, and by making it less than or equal to the above upper limit value, it is possible to suppress the relative reduction in the ratio of other components. A tendency to cause a decrease in sensitivity, plate-making properties, etc. 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, still more preferably 1 to 15% by mass, still more preferably 2 to 10% by mass, particularly preferably 2 to 5 mass %.

Moreover, the content ratio of the (f) dispersant to 100 parts by mass of the colorant (a) 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 Below, it is especially preferable that it is 30 mass parts or less. By making the content ratio of the dispersant (f) more than or equal to the above lower limit value, sufficient dispersibility tends to be easily obtained, and by making it less than or equal to the above upper limit value, it is possible to suppress the relative reduction in the ratio of other components. A tendency to cause a decrease in sensitivity, plate-making properties, etc. As a combination of an upper limit and a lower limit, for example, 5-50 mass parts is preferable, 10-50 mass parts is more preferable, 15-30 mass parts is still more preferable.

In the case of using an adhesion improving agent, the content ratio is usually 0.1 to 5 mass %, preferably 0.2 to 3 mass %, and more preferably 0.4 to 2 mass % in the total solids in the photosensitive coloring composition. %. By making the content ratio of the adhesion improver more than the above lower limit value, the effect of improving the adhesion tends to be sufficiently obtained, and by making it equal to or less than the above upper limit value, it is possible to suppress a decrease in sensitivity or residues remaining after image development. The tendency to become a condition of defect.

Moreover, when using a surfactant, its content rate is 0.001-10 mass % normally in the total solid content in the photosensitive coloring composition, Preferably it is 0.005-1 mass %, More preferably, it is 0.01 to 0.5 mass %, preferably 0.03 to 0.3 mass %. By setting the content ratio of the surfactant to be more than the above lower limit value, the smoothness and uniformity of the coating film tend to be easily expressed, and by setting the content ratio of the surfactant to be equal to or less than the above upper limit value, the coating film tends to be easily expressed. Its 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 for forming a coloring spacer. From the viewpoint of use as a coloring spacer, it is preferable that the optical density (OD) per 1 μm of the film thickness of the cured film is high. The coloring spacer obtained by curing the photosensitive coloring composition of the present invention alone 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, particularly preferably 0.10 More than 0.15 is more preferable. Here, the optical density (OD) per 1 μm of film thickness is a value measured by the method described in the Examples described below.

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

Furthermore, the photosensitive coloring composition of the present invention is preferably such that the ratio of the average absorbance at a wavelength of 400 to 500 nm to the average absorbance at a wavelength of 500 to 700 nm is 1.8 or more, more preferably 2.0 or more, and still more preferably 3.0 or more, Moreover, 15 or less are preferable, 10 or less are more preferable, 7 or less are still more preferable, and 4.5 or less are especially preferable. By setting it as the said lower limit or more, there exists a tendency for the color tone close to black to be obtained when it is laminated with a blue color filter. Moreover, there exists a tendency for an optical density (OD) to be improved by setting it as below the said upper limit.

Here, the ratio of the average absorbance at a wavelength of 400 to 500 nm of the photosensitive coloring composition with respect to the average absorbance at a wavelength of 500 to 700 nm can be used to form a cured film with a film thickness of 2.5 μm using the photosensitive coloring composition. Spectrophotometer is determined by measuring absorbance at wavelengths of 400 to 700 nm at 1 nm intervals. The detailed measurement conditions etc. are not specifically limited, For example, it can measure by the following method. First, the photosensitive coloring composition was apply|coated on a glass substrate ("AN100" by AGC company) using a spin coater. Next, the coating film was formed by heating and drying on a hot plate at 90° C. for 90 seconds. The obtained coating film was irradiated with ultraviolet rays in the air. Ultraviolet light with 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, using a developer 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), a water pressure of 0.15 MPa was applied at 25°C. After the shower development, the development was stopped with pure water and washed with water spray. The spray developing time was adjusted between 10 and 120 seconds, and was set to be 1.5 times the time for dissolving and removing the unexposed coating film. The substrate with the 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 with a film thickness of 2.5 μm. Then, using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation, the absorbance of the substrate at a wavelength of 400 to 700 nm was measured at 1 nm intervals, and the glass substrate not coated with the photosensitive coloring composition was used as a control. Calculate the average absorbance by averaging the measured values of absorbance at wavelengths of 400 to 500 nm at intervals of 1 nm. Similarly, calculate the average absorbance at wavelengths of 500 to 700 nm, and then calculate the average absorbance at wavelengths of 400 to 500 nm relative to the wavelength. The ratio of the average absorbance between 500 and 700 nm.

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

x is 0.40 or more, preferably 0.42 or more, more preferably 0.45 or more, and still more preferably 0.46 or more. Moreover, x is 0.55 or less, preferably 0.53 or less, more preferably 0.52 or less, still more preferably 0.51 or less, particularly preferably 0.50 or less. By setting the above lower limit value or more, sufficient light-shielding properties can be ensured, and the transmittance at wavelengths of 400 to 500 nm tends to be suppressed, and by setting the above upper limit value or less, mechanical properties tend to be improved. . As a combination of an upper limit and a lower limit, for example, 0.42-0.53 is preferable, 0.45-0.52 is more preferable, 0.46-0.51 is still more preferable, 0.46-0.50 is especially preferable.

Moreover, y is 0.35 or more, Preferably it is 0.37 or more, More preferably, it is 0.40 or more, More preferably, it is 0.41 or more, Especially preferably, it is 0.42 or more. Moreover, y is 0.50 or less, Preferably it is 0.48 or less, More preferably, it is 0.47 or less, More preferably, it is 0.46 or less, More preferably, it is 0.45 or less. By setting the above lower limit value or more, sufficient light-shielding properties can be ensured, and the transmittance at wavelengths of 400 to 500 nm tends to be suppressed, and by setting the above upper limit value or less, mechanical properties tend to be improved. . As a combination of an upper limit and a lower limit, for example, 0.37-0.48 is preferable, 0.40-0.47 is more preferable, 0.41-0.46 is still more preferable, 0.42-0.45 is especially preferable.

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 the photosensitive coloring composition and measuring the spectral spectrum. The detailed measurement conditions etc. are not specifically limited, For example, it can measure by the following method. First, the photosensitive coloring composition was apply|coated on a glass substrate ("AN100" by AGC company) using a spin coater. Next, the coating film was formed by heating and drying on a hot plate at 90° C. for 90 seconds. The obtained coating film was irradiated with ultraviolet rays in the air. Ultraviolet light with 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, using a developer 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), a water pressure of 0.15 MPa was applied at 25°C. After the shower development, the development was stopped with pure water and washed with water spray. The spray developing time was adjusted between 10 and 120 seconds, and was set to be 1.5 times the time for dissolving and removing the unexposed coating film. The substrate with the 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 with a film thickness of 1.0 μm. Next, regarding the light transmittance of this substrate, the transmittance of wavelengths 380 to 780 nm was measured at intervals of 1 nm using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation, and the glass that was not coated with the photosensitive coloring composition was used. The substrate served as a control. Then, according to JIS Z8701, the chromaticity coordinates (x, y) of the xy chromaticity diagram in the XYZ colorimetric system were calculated according to the transmittance of the wavelength of 380-780 nm and the distribution (luminescence spectrum) of the light source 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. Generally, it is preferable to disperse the (a) colorant in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (a) colorant is micronized by the dispersion treatment, the coating properties of the photosensitive coloring composition are improved.

The dispersion treatment is usually preferably carried out by a system in which (a) a colorant, (e) a solvent, and (f) a dispersant, and optionally (b) a part or all of an alkali-soluble resin are used together (hereinafter, it may be used in some cases). The mixture of dispersion treatment, and the composition obtained by this treatment are called "ink" or "pigment dispersion"). In particular, when a polymer dispersant is used as the (f) dispersant, the viscosity increase over time (excellent dispersion stability) of the obtained ink and photosensitive coloring composition can be suppressed, which 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 can be preferably used as those described as usable for the photosensitive coloring composition, respectively.

Furthermore, when the liquid containing all the components formulated in the photosensitive coloring composition is subjected to dispersion treatment, since heat is generated during the dispersion treatment, there is a possibility of modification of highly reactive components. Therefore, it is preferable to carry out the dispersion treatment by a system that does not contain (c) a photopolymerization initiator or (d) an ethylenically unsaturated compound. In the case of dispersing the (a) colorant by a sand mill, glass beads or zirconia beads with a particle size 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 room temperature to 80°C. The dispersion time tends to be different depending on the composition of the liquid, the size of the dispersion treatment device, etc., and the appropriate time may be adjusted appropriately. The standard of 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 as the above lower limit value or more, it tends to suppress that the dispersion treatment is insufficient and the coarse pigment ((a) colorant) particles remain, and the developability, adhesiveness, resolution, etc. tend to be deteriorated easily. full. Moreover, by setting it as the said upper limit or less, it exists in the tendency to suppress that a pigment is crushed and generate|occur|produce a large amount of ultrafine particles, and the dispersion stability becomes favorable.

In addition, the dispersed particle size 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. Next, the ink obtained by the above-mentioned dispersion treatment and the above-mentioned other components contained in the photosensitive coloring composition are mixed to prepare a uniform solution. In the production process of the photosensitive coloring composition, since fine dirt is often mixed into the liquid, it is preferable to filter the obtained photosensitive coloring composition with a filter or the like.

[Cure] The cured product of the present invention can be obtained by curing the photosensitive coloring composition of the present invention. The hardened|cured material which hardened the photosensitive coloring composition can be used suitably as a coloring spacer.

[Colored Spacer] The colored spacer of the present invention including the cured product of the present invention will be described below.

(1) Support The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, and as a material, for example, polyester-based resins such as polyethylene terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polysilicon are exemplified. Thermoplastic resin sheets such as epoxy resins, unsaturated polyester resins, poly(meth)acrylic resins and other thermosetting resin sheets, or various glasses. Among them, from the viewpoint of heat resistance, glass and heat-resistant resin are preferred. In addition, transparent electrodes such as ITO (Indium Tin Oxide, indium tin oxide) and IZO (Indium Zinc Oxide, indium zinc oxide) are also formed on the surface of the substrate. In addition to the transparent substrate, it can also be formed on a TFT array.

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

(2) Colored spacer The photosensitive coloring composition of the present invention can be used in the same application as a known photosensitive coloring composition for color filters. Hereinafter, when it is used as a coloring spacer, the formation method will be described. .

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

(3) Formation of coloring spacer [1] Supply method to substrate The photosensitive coloring composition of the present invention is usually supplied to a support in a state of being dissolved or dispersed in a solvent. As the supply method, it can be performed by a conventionally known method, for example, a spin coating method, a wire 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 can also be supplied in a pattern by an ink jet method, a printing method, or the like. Among them, the die coating method can significantly reduce the usage amount of the coating liquid, and is not affected by the fog attached at the spin coating method at all, 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, particularly preferably in the range of 1 μm to 7 μm. range of μm. In addition, it is important that the dry film thickness or the height of the spacer finally formed is uniform over the entire area of the substrate. When the deviation is large, there is a situation in which defects such as display unevenness occur in the liquid crystal panel.

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

In addition, a well-known board|substrate, such as a glass substrate, can be used as a support body. In addition, it is preferable that the surface of the substrate is flat.

[2] Drying method Drying after supplying the photosensitive coloring composition to the support is preferably a drying method using a hot plate, an IR (infrared) oven, or a convection oven. Moreover, it is also possible to combine a drying method under reduced pressure in which drying is performed in a reduced pressure chamber without raising the temperature.

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

[3] Exposure method Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet light or visible light through the mask pattern. In the case of exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or disposing the exposure mask at a position away from the coating film of the photosensitive coloring composition, and A method of projecting exposure light through the exposure mask. Moreover, the scanning exposure method by laser light which does not use a mask pattern can also be used. At this time, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, exposure may be performed in a deoxidized environment as necessary, or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

As a preferred aspect of the present invention, in the case of simultaneously forming colored spacers with different heights by photolithography, for example, an exposure mask having a light-shielding portion (light transmittance of 0%) and a plurality of The openings with the highest average light transmittance (completely transmitted openings) and the openings with lower average light transmittances (intermediately transmitted openings). With this method, the difference in residual film ratio is generated by the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount. For example, a method of fabricating a matrix-like light-shielding pattern using light-shielding units having minute polygons is known as the intermediate transmission opening. Moreover, the method of controlling light transmittance by the film of materials, such as chromium type|system|group, molybdenum type|system|group, tungsten type, and silicon type|system|group as an absorber, is known.

The light source used for the above exposure is not particularly limited. Examples of the light source include light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps, or argon ion lightning. Laser, YAG (Yttrium Aluminum Garnet, yttrium-aluminum-garnet) laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, near-infrared semiconductor laser and other laser light sources. In the case of irradiating light of a specific wavelength and using it, an optical filter can also be used.

The optical filter can be, for example, a type that can control the light transmittance at the exposure wavelength by a thin film, and as a material in this case, for example, Cr compounds (Cr oxides, nitrides, oxynitrides, 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, preferably 200 mJ/cm 2 ² or less, more preferably 150 mJ/cm ² or less. In addition, in the case of the proximity exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm Below, it is more preferable that it is 300 micrometers or less.

[4] Development method After the above-mentioned exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution may further contain surfactants, organic solvents, buffers, complexing agents, dyes or pigments.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, 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, etc. basic compounds. These basic compounds may be a mixture of two or more.

As said surfactant, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters are mentioned. Nonionic surfactants such as esters; anionics such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinates Surfactant; amphoteric surfactant such as alkyl betaine and amino acid.

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

The conditions of the development treatment are not particularly limited. Usually, the development temperature can be in the range of 10 to 50°C, preferably 15 to 45°C, especially 20 to 40°C, by immersion development method, spray development method, It is carried out by any developing method such as brush developing method and ultrasonic developing method.

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

The size or shape of the coloring spacer of the present invention is appropriately adjusted according to the specifications of the color filter to which it is applied. Colored spacers with different spacer heights are useful. In this case, the height of the spacers is usually about 2 to 7 μm, and the auxiliary spacers usually have a height of about 0.2 to 1.5 μm lower than the spacers.

[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 coloring layers are laminated on a glass substrate as a transparent substrate. And surface coating, and after forming coloring spacers, forming alignment film and manufacturing. Alternatively, the pixel coloring layer and the coloring spacer may be formed on the liquid crystal driving side substrate, or may be separately formed on the transparent substrate and the liquid crystal driving side substrate. In addition, as described in Korean 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 can also be provided in the non-display area The spacer, in this case, can reduce the leakage of light to the non-display area by laminating the color filter of the blue layer or the red layer on the opposite side. Moreover, only a blue layer, only a red layer, and only a green layer may be sufficient. A liquid crystal display with an LED backlight device tends to have a strong blue light component from the LED. Therefore, the component of blue light is easily transmitted. For example, in the case of only a single layer, especially only a blue layer, light leakage with a wavelength of 400 to 500 nm tends to occur easily. This light leakage can be adjusted by the laminated structure when a liquid crystal display is produced, or the material properties of the opposing coloring spacers, for example, it is suitable to use a coloring 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 coloring spacer of the present invention. For example, a liquid crystal cell can be formed by laminating the above-mentioned color filter having the colored spacer of the present invention with a liquid crystal drive side substrate, and by injecting liquid crystal into the formed liquid crystal cell, a color filter having the colored spacer of the present invention can be produced. The image display device of the present invention, such as a liquid crystal display device. [Example]

Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example unless the summary is exceeded. The components of the photosensitive coloring compositions used in the following Examples and Comparative Examples are as follows.

<Alkali-soluble resin-I> It heated up to 120 degreeC, stirring 145 mass parts of propylene glycol monomethyl ether acetates with nitrogen substitution. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 3 hours passed. 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 container 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. Then, 56.2 mass parts of tetrahydrophthalic anhydride (THPA) and 0.7 mass parts of triethylamine were added, and it was made to react at 100 degreeC for 3.5 hours. The thus obtained alkali-soluble resin-I had a weight-average molecular weight Mw in terms of polystyrene measured by GPC of 8400, and an acid value of 80 mgKOH/g.

<Alkali-Soluble Resin-II> 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 was stirred with nitrogen, and the temperature was raised to 120°C. Over 3 hours, 3.52 parts by mass of benzyl methacrylate, 68.8 parts by mass of methacrylic acid, 39.7 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 2 parts by mass were added dropwise thereto. , The mixed solution of 3.3 parts by mass of 2'-azobis-2-methylbutyronitrile was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 38.4 parts by mass of glycidyl methacrylate, 0.8 part by mass of tris(dimethylaminomethyl)phenol, and 0.1 part by mass of hydroquinone were added, and the reaction was continued at 100° C. for 12 Hour. The alkali-soluble resin-II thus obtained had a weight-average molecular weight Mw in terms of polystyrene measured by GPC of 19100, and an acid value of 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 prepared at 85° C. part and 350 parts by mass of dipentaerythritol polyacrylate (A-9550 manufactured by Shin-Nakamura Chemical Co., Ltd.) for 6 hours to obtain a polyfunctional acrylate (d) having one carboxyl group and two or more acrylyl groups in one molecule. -1). Next, at 80° C., 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 , 0.2 g of 6-tetramethylpiperidine 1-oxyl radical, 8.0 g of triphenylphosphine, and 18.9 g of propylene glycol monomethyl ether acetate were stirred until the acid value became 2 mgKOH/g or less. Next, 161.6 g of propylene glycol monomethyl ether acetate was added to 520.5 g of the obtained reaction product and dissolved, and then 24.2 g of 1,2,3,6-tetrahydrophthalic anhydride was added, and the reaction was carried out at 90°C. 4 hours, whereby alkali-soluble resin-III was obtained. The acid value of the obtained alkali-soluble resin-III was 23 mgKOH/g, the weight average molecular weight Mw in terms of polystyrene measured by GPC was 3000, and the double bond equivalent was 120 g/mol.

<Dispersant-I> "BYK-LPN21116" manufactured by BYK-Chemie (including A block with quaternary ammonium salt group and tertiary amine group in the side chain and A block without quaternary ammonium salt group and tertiary amine group) Acrylic A-B block copolymer of B block. Amine value is 70 mgKOH/g. Acid value is 1 mgKOH/g or less) The A block of Dispersant-I contains the following formulas (1a) and (2a) The repeating unit contains the repeating unit of the following formula (3a) in the B block. The content ratios of the repeating units of the following formulae (1a), (2a), and (3a) in the total repeating units of the dispersant-I were 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[Chemical 50]

<Dispersant-II> "DISPERBYK-2000" manufactured by BYK-Chemie Co., Ltd. (copolymerization of acrylic A-B block including A block with quaternary ammonium salt group in side chain and B block without quaternary ammonium salt group The amine value is 10 mgKOH/g. The 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 (methacryloyl-containing phosphate ester) manufactured by Nippon Kayaku Co., Ltd. <Additive- II> SH6040 (3-glycidoxypropyltrimethoxysilane) manufactured by Dow Corning Toray Co., Ltd. <Surfactant> MEGAFAC F-554 manufactured by DIC Corporation

之氧化鋯珠，並添加分散液之2.5倍之質量。分散結束後，藉由過濾器將珠粒與分散液分離，而製備顏料分散液1～6。<Preparation of Pigment Dispersion Liquids 1 to 6> The pigments, dispersants, alkali-soluble resins, and solvents described in Table 2 were mixed so that the mass ratios described in Table 2 might be obtained. In addition, the amount of the dispersant and alkali-soluble resin in Table 2 is the amount of the solid content, and the amount of the solvent also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. The solution was subjected to dispersion treatment in the range of 25 to 45° C. for 3 hours by means of a paint shaker. As beads, use 0.5 mm

of 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> Pigment dispersion liquid 7 was prepared by dispersing in the same manner as 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 content, and the amount of the solvent 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 Violet 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 above, the total solid content of the photosensitive coloring composition was Each component was added so that the ratio in Tables 3 to 5 would be the mixing ratio, and the solvent was added so that the content ratio of the total solid content was 22% by mass and PGMEA/MB=80/20 (mass ratio), It stirred and melt|dissolved, and the photosensitive coloring composition 1-14 was prepared. Using each of the obtained photosensitive coloring compositions, evaluation was performed by the method described below.

[table 3]

[Table 4]

[table 5]

<Measurement of chromaticity> Each photosensitive coloring composition was apply|coated on a glass substrate ("AN100" by AGC company) using a spin coater so that the film thickness after heating and baking might become 1.0 micrometers. Next, the coating film was formed by heating and drying on a hot plate at 90° C. for 90 seconds. About the obtained coating film, the whole exposure process was performed without using a photomask. Ultraviolet light with 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 . In addition, ultraviolet irradiation is performed under the air.

Next, using a developer 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), a water pressure of 0.15 MPa was carried out at 25°C. After the shower development, the development was stopped with pure water and washed with water spray. The shower developing time was set to develop for 50 seconds. This board|substrate was hardened by heating and baking at 230 degreeC for 20 minutes in an oven, and the board|substrate for chromaticity measurement which has a colored layer was obtained.

Using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation, the light transmittance of each obtained substrate for chromaticity measurement at a wavelength of 380 to 780 nm was measured at intervals of 1 nm, and the light transmittance was measured at a wavelength of 380 to 780 nm without coating of the photosensitive coloring composition. A glass substrate served as a control. Then, the chromaticity coordinates of the xy chromaticity diagram in the XYZ colorimetric system (x , y). The results are shown in Tables 3 to 5.

<Preparation of the substrate for optical property evaluation> Each photosensitive coloring composition was apply|coated on the glass substrate ("AN100" by AGC company) using a spin coater so that the film thickness after heating and baking might become 2.5 micrometers. Next, the coating film was formed by heating and drying on a hot plate at 90° C. for 90 seconds. About the obtained coating film, the whole exposure process was performed without using a photomask. Ultraviolet light with 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 . In addition, ultraviolet irradiation is performed under the air.

Next, using a developer 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), a water pressure of 0.15 MPa was carried out at 25°C. After the shower development, the development was stopped with pure water and washed with water spray. The shower developing time was set to develop for 50 seconds. This board|substrate was hardened by heating and baking at 230 degreeC for 20 minutes in an oven, and the board|substrate for optical characteristic evaluation which has a colored layer was obtained.

<Preparation of a blue substrate> Using the pigment dispersion liquid 6 prepared above, each component was added so that the ratio in the total solid content of the photosensitive coloring composition became the following mixing ratio, and the total solid content was further included. PGMEA was added so that a ratio might become 22 mass %, it stirred, and melt|dissolved, and the photosensitive coloring composition 15 was prepared.

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

Then, the same operation as <Preparation of a substrate for evaluation of optical properties> was performed except that the film thickness after heating and firing was adjusted to be 1.0 μm to obtain a blue substrate having a blue layer.

<Evaluation of transmittance, absorbance, and color tone at wavelengths of 400 to 500 nm> Using a spectrophotometer UV-3150 manufactured by Shimadzu Corporation, the wavelengths of the obtained substrate for evaluation of optical properties and the blue substrate were measured at 1 nm intervals from 380 to The light transmittance and absorbance at 780 nm, and the glass substrate not coated with the photosensitive coloring composition was used as a control.

Then, the measured values of transmittance at wavelengths of 400 to 500 nm of each substrate at every 1 nm were averaged to calculate the average transmittance, and these calculated values were used to calculate the relationship between the optical property evaluation substrate and the blue The average transmittance in the state where the substrates are 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, so it is preferable that the value of the average transmittance is lowered by further laminating a coloring layer. In the same procedure, the transmittance at a wavelength of 400 nm, the transmittance at a wavelength of 450 nm, and the transmittance at a wavelength of 500 nm were calculated, and the results are shown in Tables 3 to 5.

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

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

Next, from the transmittance of each optical property evaluation substrate and the blue substrate at wavelengths of 380 to 780 nm every 1 nm and the distribution (emission spectrum) of the light source in FIG. The chromaticity coordinates (x, y) of the xy chromaticity diagram in the XYZ colorimetric system of the state of the state were evaluated according to the following criteria. Each result is shown in Tables 3-5.

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

<Evaluation of Optical Density (OD)> The optical density ( OD). From these measured values, the optical density in the state in which the colored layer and the blue layer were laminated was calculated. The results are shown in Tables 3 to 5. Next, only the optical density (OD/μm) per unit film thickness of the colored layer of the substrate for evaluation of optical properties was calculated. The results are shown in Tables 3 to 5. In addition, in Tables 3 to 5, as "optical density OD/µm", the unit optical density OD/µm per 1 µm is described.

<Preparation of the board|substrate for mechanical property evaluation> The photosensitive coloring composition of each of Examples 1-12 and Comparative Examples 1 and 2 was apply|coated on a glass substrate ("AN100" by Asahi Glass Co., Ltd.) using a spin coater. After vacuum drying, the coating film was formed by heating and drying on a hot plate at 90° C. for 90 seconds. For the obtained coating film, complete penetration openings with circular patterns of various diameters of 5 to 50 μm in diameter (5 to 20 μm: at intervals of 1 μm; 25 to 50 μm: at intervals of 5 μm) were used. Part of the exposure mask to perform exposure processing. The exposure pitch (the distance between the mask and the coated surface) was 250 μm. As 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 . In addition, ultraviolet irradiation is performed under the air.

Next, using a developer 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), a water pressure of 0.05 MPa was applied at 25°C. After the shower development, the development was stopped with pure water and washed with water spray. The spray developing time was adjusted between 10 and 120 seconds, and was set to be 1.3 times the time for dissolving and removing the unexposed coating film. By these operations, a pattern that will not require partial removal is obtained. The substrate on which the pattern was formed was heated in an oven at 230° C. for 20 minutes to harden the pattern, thereby obtaining a substantially cylindrical spacer pattern with a height of 2.5 μm.

<Evaluation of Mechanical Properties> Among the obtained spacer patterns, the elastic recovery rate was measured according to the following procedure, with respect to a pattern having a diameter of the bottom surface of 22±2 μm. As a micro hardness tester for the load-unload 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). The load was held at 100 mN for 5 seconds, then unloaded at the same speed, and the load-displacement curve was obtained when the load dropped to 0 mN for 5 seconds. Based on the load-displacement curve, the maximum displacement value was used as the maximum displacement H[max], and the displacement after the load was 0 mN and held for 5 seconds was calculated as the final displacement H[Last]. Next, the elastic recovery rate was calculated by the following formula, and the elastic recovery rate evaluation was performed 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%

The spacer patterns obtained using the photosensitive coloring compositions of Examples 1, 6 to 9, and Comparative Example 2 were carried out in the same manner as described above, except that the achieved load was changed from 100 mN to 200 mN. According to the order and conditions, the load-displacement curve was obtained, 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, by using the photosensitive coloring composition in which the content ratio of the orange pigment in all the colorants is 45% by mass or more, the wavelength of 400 to 500 nm can be obtained. The average transmittance becomes sufficiently low. The reason for this is considered to be that light with a wavelength of 400 to 500 nm that is transmitted through the blue layer without being absorbed by the orange pigment is sufficiently shielded by setting the content ratio of the orange pigment in all the colorants to be equal to or higher than the above lower limit value. . Moreover, similarly, according to the comparison of Examples 1 to 5 and Comparative Example 1, it can be seen that by making 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 for this is considered to be that by setting the chromaticity coordinates (x, y) within the above-mentioned range, that is, a colorant whose color is close to orange, the colorant can sufficiently mask the blue color. The light with a wavelength of 400 to 500 nm that is not absorbed but transmitted through the layer.

Furthermore, from the comparison of Examples 1-5 and the comparative example 1, when using the photosensitive coloring composition whose content rate of the orange pigment in all colorants is 45 mass % or more, the color tone is practically sufficient. The reason for this is that by adding the hue of the coloring layer to the hue of the blue layer, the hue is uniform and close to black. In addition, from the comparison of Examples 2 and 3 and Example 4, it was found that the lower the content ratio of the blue pigment and the violet pigment in all the colorants, the better the color tone. The reason for this is also to add the hue of the colored layer to the hue of the blue layer.

In Table 4, from the comparison of Examples 6 to 9 and Comparative Example 2, it can be seen 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 coloring spacer is less than 23% by mass. Mechanical properties become good. It is considered that by setting the content ratio of the coloring agent in the total solid content to 23% by mass or less, the content ratio of the coloring agent that does not undergo elastic deformation is prevented from becoming too high, and the coloring spacer can be suppressed from being under a load. Plastic deformation, the elastic recovery rate becomes good. Moreover, according to the comparison of Examples 6 to 9, regardless of the content ratio of the coloring agent in the total solid content, by setting the content ratio of the orange pigment in the total colorant to 45% by mass or more, the reduction can be sufficiently reduced. Average transmittance at wavelengths of 400 to 500 nm.

Furthermore, according to Examples 1 to 5 in Table 3 and Examples 10 and 11 in Table 5, regardless of the type of the coloring agent contained other than the orange pigment, the content ratio of the orange pigment in the coloring agent was set to 45 Mass % or more, the average transmittance at a wavelength of 400 to 500 nm becomes sufficiently low. In addition, it was found that the mechanical properties of the coloring spacer 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 regardless of the type of the coloring agent contained other than the orange pigment. well.

Furthermore, according to the comparison between Example 1 in Table 3 and Example 12 in Table 5, regardless of the type of the orange pigment, by setting the content ratio of the orange pigment in the colorant to 45% by mass or more, the wavelengths of 400 to 500 The average transmittance of nm can be reduced sufficiently. Moreover, it turned out that the mechanical property of a coloring spacer becomes favorable by making the content rate of the coloring agent in the total solid content of the photosensitive coloring composition 23 mass % or less irrespective of the kind of orange pigment.

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

Claims (12)

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, and has In the total solid content of the coloring composition, the content ratio of the above-mentioned (a) colorant is 23% by mass or less, the above-mentioned (a) colorant contains an orange pigment, and the content ratio of the above-mentioned orange pigment in the above-mentioned (a) colorant is: 45 mass % or more, and the content ratio of the total of the blue pigment and the violet pigment in the said (a) colorant is 20 mass % or less. The photosensitive coloring composition of Claim 1 whose content rate of the said orange pigment in the said (a) coloring agent is 80 mass % or more. The photosensitive coloring composition of 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 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 of any one of Claims 1-3 whose content rate of the said (a) coloring agent in the total solid content of the photosensitive coloring composition is 1 mass % or more. The photosensitive coloring composition according to any one of claims 1 to 3, which is used to form a coloring 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, and has In the total solid content of the coloring composition, the content ratio of the above-mentioned (a) colorant 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, and the total content ratio of the blue pigment and the violet pigment in the above-mentioned (a) colorant is 20 mass % or less. The photosensitive coloring composition according to claim 8, wherein in the colorant (a), the content ratio of the orange pigment is 45 mass % or more, the content ratio of the red pigment is 1 mass % or more, or the content ratio of the yellow pigment is 1 mass % or more mass % or more. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 9. A colored spacer comprising the hardened material of claim 10. An image display device provided with the coloring spacer as claimed in claim 11.

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