KR20210105876A - Photosensitive coloring composition, cured product, colored spacer, and image display device - Google Patents

Abstract

A photosensitive coloring composition capable of forming a colored spacer having excellent surface roughness and mechanical properties is provided. The photosensitive coloring composition of this invention is a photosensitive coloring composition containing (a) a coloring agent, (b) alkali-soluble resin, (c) a photoinitiator, and (d) an ethylenically unsaturated compound, Comprising: The containing of said (a) coloring agent A ratio is 2-20 mass % in the total solid of the photosensitive coloring composition, the said (a) coloring agent contains a purple pigment, and the content rate of the said purple pigment in the said (a) coloring agent is 50 mass % or more.

Description

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

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

The entire contents of the specification, claims, drawings, and abstracts of Japanese Patent Application No. 2018-236121 filed with the Japan Patent Office on December 18, 2018, and part or all of the contents disclosed in documents cited in this specification, etc., are hereby incorporated herein by reference. It is cited and incorporated as the disclosure of this specification.

A liquid crystal display (LCD) utilizes the property that the arrangement method of liquid crystal molecules is changed by on/off of the voltage with respect to liquid crystal. Each member which comprises a liquid crystal panel is formed by the method using the photosensitive composition typified by photolithography in many cases. As an example, what is used in order to keep the space|interval of the board|substrate of 2 sheets in a liquid crystal panel constant, what is called a spacer is mentioned.

Conventionally, when a transparent spacer is used for a TFT-type LCD, the TFT as a switching element may cause malfunction by the light which penetrated the spacer. In order to prevent this, for example, Patent Document 1 describes a method of using a spacer (colored spacer) having light-shielding properties. In addition, in Patent Document 2, after securing light-shielding properties and voltage retention of liquid crystals, in order to obtain a colored spacer that can control the shape and level difference and has excellent adhesion to the substrate, a colored photosensitive composition containing a pigment of a specific combination. It is suggested to use

In addition, since the liquid crystal panel is manufactured through a step of pressing between two substrates under high temperature and high pressure, it is required that the spacer is not deformed even by the high temperature and high pressure conditions at the time of pressing and that the spacer function is maintained. That is, even if it is deformed by external pressure, mechanical properties such as recovery rate and elastic recovery rate are required to return to the original shape when external pressure is excluded. For example, it is described in patent document 3 that the mechanical property in a high film thickness becomes high by using a specific photoinitiator, and, in patent document 4, mechanical property is improved by using a specific unsaturated group containing compound. rising is described.

On the other hand, patent document 5 describes that the contamination of the liquid-crystal layer by a coloring agent is reduced by using the coloring composition containing a purple coloring agent and/or a brown coloring agent, and a specific blue coloring agent.

Japanese Patent Laid-Open No. 8-234212 International Publication No. 2013/115268 Japanese Laid-Open Patent Publication No. 2015-38607 Japanese Laid-Open Patent Publication No. 2005-165294 Japanese Laid-Open Patent Publication No. 2018-9132

In order to suppress the display defect of a liquid crystal display, the surface roughness of a colored spacer is low and it is necessary to be excellent in smoothness.

As a result of the present inventors examining, it became clear with the photosensitive coloring composition of patent document 2 and 5 that it was difficult to obtain the colored spacer which made surface roughness and mechanical characteristic compatible.

In Patent Documents 3 and 4, there is no description regarding the colored spacer, and the influence of the colorant in the spacer is unknown.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition capable of forming a colored spacer excellent in surface roughness and mechanical properties.

As a result of the present inventors earnestly examining in order to solve the said subject, the content rate of the coloring agent in total solid should be within a specific range, and using a specific pigment as a coloring agent, By making the content rate into a specific range, the said subject found out what could be solved, and led to the present invention.

That is, the present invention has the following structures [1] to [9].

[1] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photoinitiator, and (d) an ethylenically unsaturated compound,

The content rate of the said (a) coloring agent is 2-20 mass % in the total solid of the photosensitive coloring composition,

(a) the colorant comprises a purple pigment, and

The content rate of the said purple pigment in the said (a) coloring agent is 50 mass % or more, The photosensitive coloring composition characterized by the above-mentioned.

[2] The photosensitive coloring composition according to [1], wherein the purple pigment contains at least one selected from the group consisting of C. I. Pigment Violet 29 and C. I. Pigment Violet 23.

[3] The photosensitive coloring composition according to [1] or [2], wherein the (a) colorant further contains an orange pigment.

[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the content ratio of the alkali-soluble resin (b) to 100 parts by mass of the (d) ethylenically unsaturated compound is 150 parts by mass or less.

[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the (c) photoinitiator contains a hexaarylbiimidazole compound.

[6] The photosensitive coloring composition according to any one of [1] to [5], which is for forming a colored spacer.

[7] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [6].

[8] A colored spacer composed of the cured product according to [7].

[9] An image display device comprising the colored spacer according to [8].

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive coloring composition which can form the colored spacer excellent in surface roughness and mechanical properties, a hardened|cured material, the colored spacer comprised from it, and also the image display apparatus provided with such a colored spacer can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described concretely, this invention is not limited to the following embodiment, It can implement with various changes within the range of the summary.

In addition, in this invention, "(meth)acryl" means "acryl and/or methacryl", and it is the same also about "(meth)acrylate" and "(meth)acryloyl."

"(co)polymer" means including both a homopolymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydride)... Acid" means containing both an acid and its anhydride. In addition, in this invention, "acrylic resin" means the (co)polymer containing (meth)acrylic acid, and the (co)polymer containing the (meth)acrylic acid ester which has a carboxyl group.

In addition, in this invention, "monomer" is a term opposite to what is called a high molecular substance (polymer), and it is a meaning including a dimer, a trimer, an oligomer, etc. in addition to the narrow monomer (monomer).

In this invention, "total solid content" shall mean all components other than a solvent contained in the photosensitive coloring composition or the ink mentioned later.

In this invention, a "weight average molecular weight" refers to the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).

In addition, in the present invention, unless otherwise specified, the term "amine number" refers to an amine value in terms of effective solid content, and is a value expressed by the amount of base per 1 g of solid content of the dispersant and the mass of equivalent KOH. In addition, a measurement method is mentioned later. In addition, unless otherwise indicated, an "acid value" shows an acid value in terms of effective solid content, and is computed by neutralization titration.

In addition, in this specification, the percentage and part represented by "mass" have the same meaning as the percentage and part represented by "weight".

In addition, in this specification, although the specific example of a pigment may be shown by a pigment number, "C. Terms such as "I. Pigment Red 2" mean a color index (C.I.).

[Photosensitive Coloring Composition]

The photosensitive coloring composition of the present invention,

(a) colorants

(b) alkali-soluble resin

(c) photoinitiator

(d) ethylenically unsaturated compounds

as an essential component, and if necessary, further adhesion improvers such as silane coupling agents, surfactants (applicability improvers), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, development improving agents, ultraviolet rays It contains other compounding components, such as an absorbent and antioxidant, and each compounding component is normally used in the state melt|dissolved or disperse|distributed to the solvent.

<(a) Colorant>

The photosensitive coloring composition of this invention contains (a) a coloring agent. (a) By containing a coloring agent, when using for the use which forms light-shielding members, such as moderate light absorption, especially a colored spacer, moderate light-shielding property can be acquired.

Moreover, in the photosensitive coloring composition of this invention, the content rate of (a) coloring agent is 2-20 mass % in total solid. Thus, by containing (a) a specific amount of a coloring agent, the hardened|cured material obtained, especially a colored spacer WHEREIN: It becomes possible to make light-shielding property and high mechanical characteristic compatible.

(a) Although the content rate of a coloring agent will not be specifically limited if it is 2-20 mass % in total solid, From a light-shielding viewpoint, 3 mass % or more is preferable, 4 mass % or more is more preferable, 5 mass % or more This is more preferable. On the other hand, from a viewpoint of a mechanical property, 18 mass % or less is preferable, 15 mass % or less is more preferable, 12 mass % or less is still more preferable, 10 mass % or less is still more preferable, 8 mass % or less is Especially preferred. For example, 3-18 mass % is preferable, 3-15 mass % is more preferable, 4-12 mass % is still more preferable, 4-10 mass % is still more preferable, 5-8 mass % is more preferable Especially preferred.

(a) As a coloring agent, a pigment may be used and dye may be used for it. Among these, it is preferable to use a pigment from a durable viewpoint.

The photosensitive coloring composition of this invention WHEREIN: (a) a coloring agent contains a purple pigment, and the content rate of the said purple pigment in (a) coloring agent is 50 mass % or more. It is thought that the solubility with respect to the developing solution at the time of image development becomes uniform, and surface roughness becomes favorable because dispersion|distribution of the pigment in a coating film becomes uniform by including a purple pigment in 50 mass % or more in (a) coloring agent. Moreover, since a purple pigment has the maximum absorption wavelength of an absorption peak in the wavelength vicinity of 500-600 nm in an absorption spectrum, it is effective also at the point which makes it easy to make optical density (OD) high by including a purple pigment. On the other hand, since there is little absorption with a wavelength of less than 400 nm, there is little overlap with the absorption wavelength of (c) photoinitiator, and it is effective also from a viewpoint of photocurability and a sensitivity. Moreover, since there is little absorption of wavelength 450nm, it is effective also from a viewpoint of the light resistance with respect to the blue light strongly irradiated from the backlight of a liquid crystal display.

As a purple pigment, CI Pigment Violet 1, 1 : 1, 2, 2 : 2, 3, 3 : 1, 3: 3, 5, 5 : 1, 14, 15, 16, 19, 23, 25, 27 , 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among these, from a light-shielding viewpoint, Preferably C.I. Pigment Violet 19, 23, 29, More preferably, C. I. Pigment Violet 23, 29 is mentioned. On the other hand, it is preferable to use C.I. Pigment Violet 29 from the viewpoint of dispersibility and light resistance.

(a) Although the content rate of the purple pigment in a coloring agent will not be specifically limited if it is 50 mass % or more, From a viewpoint of surface roughness improvement, 55 mass % or more is preferable, 58 mass % or more is more preferable, 60 mass % or more More preferably, 62 mass % or more is still more preferable, and 65 mass % or more is especially preferable. On the other hand, 90 mass % or less is preferable, 80 mass % or less is more preferable, and 75 mass % or less is still more preferable from a viewpoint of widening an absorption wavelength band using the optical characteristic of colorants other than a purple pigment. For example, 50-90 mass % is preferable, 55-90 mass % is more preferable, 58-80 mass % is still more preferable, 60-80 mass % is still more preferable, 62-75 mass % is more preferable It is especially preferable, and 65-75 mass % is especially preferable.

(a) Although the content rate of CI pigment violet 29 in a coloring agent is not specifically limited, From a viewpoint of surface roughness and light resistance improvement, 50 mass % or more is preferable, 55 mass % or more is more preferable, 60 mass % or more More preferably, 62 mass % or more is still more preferable, and 65 mass % or more is especially preferable. On the other hand, from the viewpoint of broadening the absorption wavelength band using the optical properties of colorants other than CI Pigment Violet 29, 90 mass % or less is preferable, 80 mass % or less is more preferable, and 75 mass % or less is further desirable. For example, 50-90 mass % is preferable, 55-90 mass % is more preferable, 58-80 mass % is still more preferable, 60-80 mass % is still more preferable, 62-75 mass % is more preferable It is especially preferable, and 65-75 mass % is especially preferable.

(a) The colorant may contain a colorant other than the purple pigment (hereinafter, abbreviated as "other colorant"). As another coloring agent, a pigment and dye are mentioned, A pigment is preferable from a heat resistant viewpoint, and an organic pigment is preferable from a viewpoint of color tone, photocurability, and a sensitivity.

As a pigment, organic coloring pigments, such as a yellow pigment, an orange pigment, a red pigment, a blue pigment, a green pigment, and a brown pigment, are mentioned.

As a yellow pigment, CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35 : 1, 36, 36 : 1, 37, 37 : 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62 : 1, 63, 65, 73, 74, 75, 81, 83 , 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134 , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170 , 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191 : 1, 192, 193, 194, 195, 196, 197, 198, 199 , 200, 202, 203, 204, 205, 206, 207, 208. Among these, from the viewpoint of dispersibility and reliability, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is preferable, and CI Pigment Yellow 138, 139, 150 is more preferable. , CI Pigment Yellow 139 is particularly preferable from the viewpoint of light-shielding properties.

As the orange pigment (orange pigment), CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, it is preferable to use CI pigment orange 13, 43, 64, 72 from the point of dispersibility and light-shielding property, and when hardening a photosensitive coloring composition with ultraviolet-ray, as an orange pigment, a thing with a low ultraviolet absorption rate It is preferable to use, it is more preferable to use CI pigment orange 64 and 72 from such a viewpoint, and CI pigment orange 64 is especially preferable.

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

As a blue pigment, CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27 , 28, 29, 33, 35, 36, 56, 56 : 1, 60, 61, 61 : 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be heard Among these, from a light-shielding viewpoint, Preferably CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, More preferably, CI Pigment Blue 15 : 6, 16 are mentioned.

In addition, it is preferable to use CI Pigment Blue 15:6, 16,60 from the point of dispersibility and light-shielding property, and when hardening the photosensitive coloring composition with ultraviolet-ray, as a blue pigment, a thing with a low ultraviolet absorption is used. It is preferable to do it, and it is more preferable to use CI Pigment Blue 60 from such a viewpoint. On the other hand, as described in Korean Patent Registration No. 10-1840984, it is preferable to use C. I. Pigment Blue 16 from the viewpoint of reliability, light blocking properties, and elastic recovery rate.

As a green pigment, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 can be heard Among these, preferably C.I. Pigment Green 7 and 36 from the viewpoint of dispersibility.

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

Among these organic color pigments, an orange pigment is preferable because it has an absorption band in the vicinity of a wavelength of 400 to 500 nm different from the absorption band of the purple pigment.

When an orange pigment is included, the content rate of the orange pigment in the (a) colorant is not particularly limited, but preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 20 mass% or more, 30 Mass % or more is especially preferable, 50 mass % or less is preferable, 45 mass % or less is more preferable, 40 mass % or less is still more preferable, and 35 mass % or less is especially preferable. For example, 5-50 mass % is preferable, 10-45 mass % is more preferable, 20-40 mass % is still more preferable, 30-35 mass % is especially preferable. There exists a tendency for optical density (OD) to become high by setting it as more than the said lower limit, and there exists a tendency for surface roughness to become favorable by setting it as below the said upper limit.

On the other hand, since light resistance tends to deteriorate when an orange pigment is included, from the viewpoint of improving the light resistance (a), the content ratio of the orange pigment in the colorant is preferably 50 mass% or less, and more preferably 40 mass% or less. and 30 mass % or less is more preferable, 20 mass % or less is still more preferable, 10 mass % or less is especially preferable, and 0 mass % is the most preferable.

Moreover, since surface roughness tends to deteriorate when a blue pigment is included, 50 mass % or less is preferable, as for the content rate of the blue pigment in (a) coloring agent, 40 mass % or less is more preferable, 30 mass % It is still more preferable, 20 mass % or less is still more preferable, 10 mass % or less is especially preferable, and 0 mass % is the most preferable.

When CI Pigment Blue 60 is included among blue pigments, since surface roughness tends to deteriorate, the content rate of CI Pigment Blue 60 in (a) coloring agent is preferably 50 mass % or less, and 40 mass % or less More preferably, 30 mass % or less is still more preferable, 20 mass % or less is still more preferable, 10 mass % or less is especially preferable, and 0 mass % is the most preferable.

Moreover, you may contain the black pigment as another coloring agent. As a black pigment, an organic black pigment and an inorganic black pigment are mentioned.

Organic black containing at least one selected from the group consisting of, for example, a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound represented by the following formula (1) as an organic black pigment pigments.

[Formula 1]

In formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom, or a chlorine atom;

R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ^- , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N= CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;

In addition, at least one combination selected from the group consisting of ^{R 2} and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ^{10 is,} may be directly bonded to each other, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR ¹¹ bridge;

R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. .

The geometric isomer of the compound represented by the general formula (1) has the following core structures (however, the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable.

[Formula 2]

When the compound represented by the general formula (1) is anionic, its charge is transferred to any known suitable cation, for example a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, transition metal , tertiary ammonium such as primary ammonium, secondary ammonium, trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated with an organometallic complex. Moreover, when the geometrical isomer of the compound represented by General formula (1) is anionic, it is preferable that it is the same salt.

In the substituents of the general formula (1) and their definitions, the following are preferable because the shielding rate tends to increase. This is because the following substituents have no absorption and are considered to have no influence on the color of the pigment.

R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom, a fluorine atom, or a chlorine atom, more preferably a hydrogen atom.

R ³ and R ⁸ are each independently preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a 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 ⁻ , and 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} Preferably, R ¹ is identical to ^{R 6 , R 2} is identical to ^{R 7 , R 3} is identical to ^{R 8 , R 4} is identical to ^{R 9 , and R 5} is identical to ^{R 10 .}

The C1-C12 alkyl group is, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n -pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1, 1,3,3-tetramethylbutyl group, 2- an ethylhexyl group, a nonyl group, a decyl group, an undecyl group, or a dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuyl group, a norbornyl group, and a boryl group. nyl group, norcaryl group, caryl group, menthyl group, norphinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.

The alkenyl group having 2 to 12 carbon atoms is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, and 1,3-butadiene- 2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2- buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group or dodecenyl group.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4(10)-tuzen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadi en-1-yl group, 7,7-dimethyl-2,4-norkaradien-3-yl group or campenyl group.

A C2-C12 alkynyl group is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, Trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octyne-8-yl group, 1-nonin-9-yl group, 1-decyne- 10-yl or 1-dodecin-12-yl.

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

The organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2) and/or a geometric isomer of the compound.

[Formula 3]

As a specific example of such an organic black pigment, Irgaphor (trademark) Black S 0100 CF (made by BASF) is mentioned as a brand name.

This organic black pigment is preferably dispersed and used by a dispersing agent, a solvent, and a method described later. In addition, the presence of a compound represented by the general formula (2) or a sulfonic acid derivative of a geometric isomer of the compound during dispersion may improve dispersibility and storage properties.

In addition, as an organic black pigment, from the viewpoint of optical properties and reliability, the organic black pigment described in Korean Patent Application Laid-Open No. 10-2018-0052502, or the organic black pigment described in Korean Patent Application Laid-Open No. 10-2018-0052864 Preference is given to using organic black pigments.

Moreover, as another organic black pigment, aniline black, cyanine black, perylene black, etc. are mentioned.

Moreover, you may use carbon black which is an inorganic black pigment. Examples of carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #144, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000 2200, #12300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, OIL7B4000, #9B4000, #140 , OIL11B, OIL30B, OIL31B

Manufactured by Degusa: Printex (registered trademark, hereinafter the same) 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

Manufactured by Cabot Corporation: Monarch (registered trademark, hereinafter the same) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, hereinafter the same) 99, REGAL99R, REGAL415, REGAL415R , REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8

Manufactured by Birla: RAVEN (registered trademark, hereinafter the same) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN850, RAVEN1020, RAVEN1020, RAVEN10U , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As carbon black, you may use what was coat|covered with resin. When carbon black coated with resin is used, there is an effect of improving the adhesiveness to the glass substrate and the volume resistance value. As carbon black coated with resin, the carbon black etc. which are described in Unexamined-Japanese-Patent No. 09-71733, etc. can be used preferably, for example. From the viewpoints of volume resistance and dielectric constant, resin-coated carbon black is preferably used.

It is preferable to disperse|distribute these pigments so that an average particle diameter may become 1 micrometer or less normally, Preferably it is 0.5 micrometer or less, More preferably, it may become 0.25 micrometer or less. Here, the standard of the average particle diameter is the number of pigment particles.

In addition, the photosensitive coloring composition WHEREIN: The average particle diameter of a pigment is the value calculated|required from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is carried out with respect to a sufficiently diluted photosensitive coloring composition (usually diluted and prepared with a pigment concentration of about 0.005-0.2 mass%. However, if there is a concentration recommended by the measuring instrument, it follows the concentration), at 25 ° C. measured in

Moreover, you may use dye other than the pigment mentioned above. Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dye include CI acid yellow 11, CI acid orange 7, CI acid red 37, CI acid red 180, CI acid blue 29, CI direct red 28, CI direct red 83, CI direct yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58 , CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7 and the like.

Examples of the anthraquinone dye include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, CI Disperse Blue 60 etc. are mentioned.

In addition, as a phthalocyanine-based dye, for example, CI Vat Blue 5 and the like, as a quinoneimine-based dye, for example, CI Basic Blue 3, CI Basic Blue 9, etc., as a quinoline-based dye, for example, CI solvent yellow 33, CI acid yellow 3, CI disperse yellow 64 etc. are mentioned as nitro type dye, for example, CI acid yellow 1, CI acid orange 3, CI disperse yellow 42, etc. are mentioned.

<(b) alkali-soluble resin>

(b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, for example, an epoxy (meth)acrylate-based resin, an acrylic resin, a carboxyl group-containing epoxy resin, a carboxyl group-containing urethane resins, novolac-based resins, polyvinylphenol-based resins, and the like,

(b1) Epoxy (meth)acrylate-based resin

(b2) acrylic copolymer resin

is preferably used from the viewpoint of excellent plate making properties. These can be used individually by 1 type or in mixture of multiple types.

<(b1) Epoxy (meth)acrylate-based resin>

(b1) The epoxy (meth) acrylate-based resin is a reaction product of an epoxy resin (epoxy compound) and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group It is a resin obtained by further reacting a polybasic acid and/or its anhydride with the hydroxyl group produced by

In addition, before reacting the polybasic acid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the resin obtained by reacting the polybasic acid and/or its anhydride is also described above. (b1) It is contained in the epoxy (meth)acrylate-type resin.

Moreover, resin obtained by making the carboxyl group of resin obtained by the said reaction react with the compound which has a functional group which can further react is also contained in the said (b1) epoxy (meth)acrylate-type resin.

As described above, the epoxy (meth) acrylate-based resin does not substantially have an epoxy group on the chemical structure, and is not limited to “(meth) acrylate”, but an epoxy compound (epoxy resin) is a raw material, and “ (meth)acrylate" is a representative example, so it is named like this according to custom.

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

<Epoxy (meth) acrylate resin (b1-1)>

Alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and/or anhydride thereof .

<Epoxy (meth) acrylate resin (b1-2)>

By adding α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polyhydric alcohol and a polybasic acid and/or anhydride thereof The obtained alkali-soluble resin.

Here, an epoxy resin shall include the raw material compound before formation of resin by thermosetting, and as this epoxy resin, it can select suitably from well-known epoxy resins and can use it. Moreover, the compound obtained by making a phenolic compound and epihalohydrin react can be used for an epoxy resin. As a phenolic compound, the compound which has a phenolic hydroxyl group more than bivalence is preferable, and a monomer or a polymer may be sufficient as it.

As the kind of epoxy resin used as a raw material, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolak type epoxy resin , naphthalene novolak-type epoxy resin, epoxy resin that is a reaction product of a polyaddition product of dicyclopentadiene and phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resin, fluorene-type epoxy resin, etc. are preferably used and those having an aromatic ring in the main chain as described above can be preferably used.

In addition, as a specific example of an epoxy resin, for example, a bisphenol A epoxy resin (For example, "jER (trademark, the same) -828" manufactured by Mitsubishi Chemical Co., Ltd., "jER-1001", "jER" -1002", "jER-1004", "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76°C), etc.), bisphenol F-type resin (e.g., "jER-807" manufactured by Mitsubishi Chemical Corporation) ”, “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 (for example, "jER-YX4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (eg, "EPPN-201" manufactured by Nippon Kayaku Corporation, "jER" manufactured by Mitsubishi Chemical Corporation) -152", "jER-154", "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolak-type epoxy resin (e.g., "EOCN (registered)" manufactured by Nippon Kayaku Co., Ltd. Trademark, hereinafter the same) -102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), trisphenolmethane Epoxy resin (for example, "EPPN (registered trademark, hereinafter the same)-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), an alicyclic epoxy resin ("Celoc" manufactured by Daicel Corporation) Side (registered trademark, hereinafter the same) 2021P", "Celoxide EHPE"), an epoxy resin obtained by glycidylating a phenol resin by reaction of dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC Corporation) ', "NC-7300" by Nippon Kayaku Co., Ltd.), the epoxy resins represented by the following general formulas (B1) to (B4), etc. can be used preferably. Specifically, as an epoxy resin represented by the following general formula (B1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "NC-3000" manufactured by Nippon Kayaku Corporation as an epoxy resin represented by the following general formula (B2), the following general As an epoxy resin represented by a formula (B4), "ESF-300" by the Shin-Nippon Steel Chemicals, etc. are mentioned.

[Formula 4]

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

[Formula 5]

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

[Formula 6]

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

[Formula 7]

In the formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ are each independently an adamantyl group which may have a substituent, a hydrogen atom, or an adamantyl group which may have a substituent A C1-C12 alkyl group or the phenyl group which may have a substituent is shown. * indicates a bond.

[Formula 8]

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

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

As α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth)acrylic acid Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2- (meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2 -(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmale Acid, 2-(meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxy Lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone are added to butylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, and (meth)acrylic acid Monomer, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate (anhydride) succinic acid, (anhydride) phthalic acid, (anhydride) maleic acid A monomer to which an acid (anhydride), such as these, was added, a (meth)acrylic acid dimer, etc. are mentioned.

Among these, (meth)acrylic acid is especially preferable from the point of surface roughness.

A well-known method can be used as a method of adding the alpha, beta-unsaturated monocarboxylic acid and/or the (alpha), beta-unsaturated monocarboxylic acid ester which has a carboxyl group to an epoxy resin. For example, in the presence of an esterification catalyst, at a temperature of 50 to 150° C., an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is reacted with an epoxy resin. can Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride. etc. can be used.

In addition, the epoxy resin, α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may all be used individually by 1 type, or 2 or more types may be used together.

The amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents based on 1 equivalent of the epoxy group of the epoxy resin, more preferably is in the range of 0.7 to 1.1 equivalents. By setting the amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group to be equal to or more than the lower limit, the shortage of the introduction amount of the unsaturated group can be suppressed, and the continuous polybasic acid and/or The reaction with the anhydride also tends to be sufficient. On the other hand, by setting it below the said upper limit, residual|survival of the unreacted material of the alpha, beta-unsaturated monocarboxylic acid and/or the alpha, beta- unsaturated monocarboxylic acid ester which has a carboxyl group can be suppressed, and hardening characteristic is easy to make good. trend is confirmed.

Examples of the polybasic acid and/or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetra. 1 or more types selected from hydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid, these anhydrides, etc. are mentioned.

Preferably, they are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or an anhydride thereof. Particularly preferably, they are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

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

Moreover, polyhydric alcohol, such as trimethylol propane, a pentaerythritol, and dipentaerythritol, is added at the time of the addition reaction of this polybasic acid and/or its anhydride, and it is good also as what introduce|transduced the multi-branched structure.

A carboxyl group-containing epoxy (meth)acrylate-based resin is usually a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, a polybasic acid and / or after mixing the anhydride, or in a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, a polybasic acid and/or its anhydride and polyvalent After mixing the alcohol, it is obtained by heating. In this case, there is no restriction|limiting in particular in the mixing order of a polybasic acid and/or its anhydride, and a polyhydric alcohol. Upon heating, a polybasic acid and/or any hydroxyl group present in a mixture of a polyhydric alcohol and a reaction product of an epoxy resin with an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group The anhydride undergoes an addition reaction.

As the carboxyl group-containing epoxy (meth)acrylate-based resin, in addition to the above, Korean Patent Application Laid-Open No. 10-2013-0022955, Korean Patent No. 10-0965189, Japanese Patent Application Laid-Open No. 2005-165294, Japanese Laid-Open The thing of patent publication 2006-312704, etc. are mentioned.

The weight average molecular weight (Mw) of the epoxy (meth)acrylate-based 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 it is 2500 or more, Usually, it is 10000 or less, Preferably it is 8000 or less, More preferably, it is 6000 or less, More preferably, it is 5000 or less, Especially preferably, it is 4000 or less. For example, 1000-10000 are preferable, 1000-8000 are more preferable, 1500-6000 are still more preferable, 2000-5000 are still more preferable, 2500-4000 are especially preferable. By setting it more than the said lower limit, there exists a tendency which can suppress that the solubility with respect to a developing solution becomes high too much, and there exists a tendency for it easy to make the solubility with respect to a developing solution good by setting it as below the said upper limit.

Although the acid value of epoxy (meth)acrylate-type resin is not specifically limited, 10 mgKOH/g or more is preferable, 20 mgKOH/g or more is more preferable, Furthermore, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 100 mgKOH/g or less is still more preferable, and 50 mgKOH/g or less is especially preferable. For example, 10-200 mgKOH/g is preferable, 10-150 mgKOH/g is more preferable, 20-100 mgKOH/g is still more preferable, 20-50 mgKOH/g is especially preferable. . By setting it as more than the said lower limit, there exists a tendency for moderate image development solubility to be acquired, and there exists a tendency which can suppress that image development progresses too much and film melt|dissolution by setting it below the said upper limit.

Although the double bond equivalent of an epoxy (meth)acrylate-type resin is not specifically limited, 800 or less are preferable, 700 or less are more preferable, 600 or less are still more preferable, 500 or less are still more preferable, 400 or less are especially Preferably, 300 or less are most preferable, 100 or more are preferable, 150 or more are more preferable, 200 or more are still more preferable, 250 or more are especially preferable. For example, 100-800 are preferable, 100-700 are more preferable, 150-600 are still more preferable, 150-500 are still more preferable, 200-400 are especially preferable, 250-300 are especially preferable. do. By using below the said upper limit, there exists a tendency for a mechanical characteristic and surface roughness to improve, Moreover, there exists a tendency for storage stability to improve by setting it as more than the said lower limit.

In addition, the double bond equivalent of resin is computable from following formula (x).

(Double bond equivalent of resin) =

(molecular weight of resin)/(number of ethylenically unsaturated double bonds per molecule of resin)...(x)

(b1) The chemical structure of the epoxy (meth) acrylate-based resin is not particularly limited, but from the viewpoint of curability, an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (i) (b1-A) (Hereinafter, it may be abbreviated as "epoxy (meth) acrylate-based resin (b1-A)") or an epoxy (meth) acrylate-based resin (b1-) having a partial structure represented by the following general formula (ii) B) (Hereinafter, it may be abbreviated as "epoxy (meth)acrylate-type resin (b1-B)") is preferable. Moreover, from a viewpoint of reliability, epoxy (meth)acrylate-type resin (b1-B) is more preferable.

[Formula 9]

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

[Formula 10]

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

(R ^b )

In the formula (i), R ^b represents a divalent hydrocarbon group which may have a substituent.

Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, a linear thing is preferable from a viewpoint of image development solubility, on the other hand, a cyclic thing is preferable from a viewpoint of image development adhesiveness. The carbon number is usually 1 or more, 3 or more are preferable, 6 or more are more preferable, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 1-20 are preferable, 3-15 are more preferable, and 6-10 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Specific examples of the divalent linear aliphatic group include a methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, a methylene group is preferable from a sclerosis|hardenable viewpoint.

Specific examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, The structure which has a sec-butyl group, a tert-butyl group, etc. is mentioned.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, Moreover, 10 or less and 5 or less are usually preferable. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit. Specific examples of the divalent cyclic aliphatic group include a hydrogen atom from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. and a group in which two were removed. Among these, a group obtained by removing two hydrogen atoms from the 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; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; nitro group; cyano group; A carboxyl group etc. are mentioned. It is preferable that it is unsubstituted from a viewpoint of synthetic|combination easiness.

Examples of the divalent aromatic cyclic group include a divalent aromatic hydrocarbon cyclic group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, 5 or more are preferable, 6 or more are more preferable, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, having two free valences. , a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

In addition, as an aromatic heterocyclic ring in a bivalent aromatic heterocyclic group, a monocyclic ring may be sufficient and a condensed ring may be sufficient. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, having two free valences. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoox sazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine and groups such as a ring, a perimidine ring, a quinazoline ring, a quinazolinone ring and an azulene ring. Among these, from a viewpoint of photocurability, the benzene ring or naphthalene ring which has two free valences is preferable, and the benzene ring which has two free valences is more preferable.

As the substituent which the 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. From a sclerosis|hardenable viewpoint, unsubstitution is preferable.

Examples of the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups in which one or more divalent aliphatic groups described above and one or more divalent aromatic cyclic groups described above are linked.

Although the number of divalent aliphatic groups is not specifically limited, Usually, 1 or more and 2 or more are preferable, Usually, 10 or less and 5 or less are preferable, and 3 or less are more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, and 2-3 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Although the number of divalent aromatic ring groups is not specifically limited, Usually, 1 or more and 2 or more are preferable, Usually, 10 or less and 5 or less are preferable, and 3 or less are more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, and 2-3 are still more preferable. There exists a tendency for sclerosis|hardenability to become favorable by setting it as more than the said lower limit, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

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

[Formula 11]

As above-mentioned, the benzene ring in Formula (i) may be further substituted by arbitrary substituents. As the 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 not specifically limited, The number may be one, and two or more may be sufficient as them.

From a viewpoint of sclerosis|hardenability, it is preferable that it is unsubstituted.

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

[Formula 12]

In formula (i-1), R ^a and R ^b have the same meaning as in the formula (i). R ^X represents a hydrogen atom or a polybasic acid residue. * indicates a bond. The benzene ring in Formula (i-1) may be further substituted by arbitrary substituents.

The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or anhydride thereof. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorend. The 1 type(s) or 2 or more types selected from an acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid are mentioned.

Among these, from the viewpoint of patterning properties, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, More preferably, they are tetrahydrophthalic acid and biphenyl tetracarboxylic acid.

One kind or two or more kinds of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate-based resin (b1-A) may be one, for example, R ^X is hydrogen An atom ^{and a polybasic acid residue in which R X} is a polybasic acid residue may be mixed.

Further, the number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate-based resin (b1-A) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less are preferable and 15 or less are more preferable. For example, 1-20 are preferable and 3-15 are more preferable. Sclerosis|hardenability exists in the tendency for sclerosis|hardenability to become favorable by setting it as more than the said lower limit, and there exists a tendency for image development solubility to become favorable by setting it as below the said upper limit.

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

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

(R ^d )

In the formula (ii), R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group or an aromatic cyclic group.

Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, Moreover, 10 or less and 5 or less are preferable normally, and 3 or less are more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, and 2-3 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Moreover, carbon number of an alicyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 30 or less are more preferable, 20 or less are still more preferable, 15 The following are particularly preferred. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are more preferable, 6-15 are still more preferable, 8-15 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferable from a viewpoint of reliability.

On the other hand, although the number of rings which an aromatic cyclic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, 3 or more are more preferable, Moreover, 10 or less, 5 or less are preferable and usually 4 or less. more preferably. For example, 1-10 are preferable, 1-5 are more preferable, 1-4 are still more preferable, 2-4 are still more preferable, 3-4 are especially preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 10 or more are still more preferable, 12 or more are especially preferable, and 40 or less are preferable, 30 or less are more preferable, 20 or less are still more preferable, and 15 or less are especially preferable. For example, 4-40 are preferable, 6-30 are more preferable, 8-20 are still more preferable, 10-15 are still more preferable, 12-15 are especially preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

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 tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, An acenaphthene ring, a fluoranthene ring, a fluorene ring, etc. are mentioned. Among these, a fluorene ring is preferable from a viewpoint of a patterning characteristic.

Moreover, the divalent hydrocarbon group in the divalent hydrocarbon group which has a cyclic hydrocarbon group as a side chain is although it does not specifically limit, For example, a divalent aliphatic group, a divalent aromatic ring group, 1 or more divalent aliphatic groups, and 1 or more 2 The group which linked the valent aromatic ring group is mentioned.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, a linear thing is preferable from a compatibility viewpoint, on the other hand, a cyclic thing is preferable from a reliability viewpoint. The carbon number is usually 1 or more, 3 or more are preferable, 6 or more are more preferable, 25 or less are preferable, 20 or less are more preferable, and 15 or less are still more preferable. For example, 1-25 are preferable, 3-20 are more preferable, and 6-15 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Specific examples of the divalent linear aliphatic group include a methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, a methylene group is preferable from a sclerosis|hardenable viewpoint.

Specific examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, The structure which has a sec-butyl group, a tert-butyl group, etc. is mentioned.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, Moreover, 10 or less, 5 or less, More preferably, 3 or less are preferable normally. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, and 2-3 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit. Specific examples of the divalent cyclic aliphatic group include a hydrogen atom from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. and a group in which two were removed. Among these, groups in which two hydrogen atoms have been removed from the adamantane ring from the viewpoint of reliability are preferable.

Examples of the substituent which the divalent aliphatic group may have include a hydroxyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; nitro group; cyano group; A carboxyl group etc. are mentioned. It is preferable that it is unsubstituted from a viewpoint of synthetic|combination easiness.

Examples of the divalent aromatic cyclic group include a divalent aromatic hydrocarbon cyclic group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, 5 or more are preferable, 6 or more are more preferable, 30 or less are preferable, 20 or less are more preferable, and 15 or less are still more preferable. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, having two free valences. , a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

In addition, as an aromatic heterocyclic ring in an aromatic heterocyclic group, a monocyclic ring may be sufficient and a condensed ring may be sufficient as it. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, having two free valences. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoox sazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine and groups such as a ring, a perimidine ring, a quinazoline ring, a quinazolinone ring and an azulene ring. Among the divalent aromatic ring groups, from the viewpoint of patterning properties, a benzene ring, a naphthalene ring or a fluorene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable.

As the substituent which the 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. From a viewpoint of image development solubility and hygroscopic resistance, unsubstitution is preferable.

Examples of the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups in which one or more divalent aliphatic groups described above and one or more divalent aromatic cyclic groups described above are linked.

Although the number of divalent aliphatic groups is not specifically limited, Usually, 1 or more and 2 or more are preferable, Usually, 10 or less and 5 or less are preferable, and 3 or less are more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, and 2-3 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Although the number of divalent aromatic ring groups is not specifically limited, Usually, 1 or more and 2 or more are preferable, Usually, 10 or less and 5 or less are preferable, and 3 or less are more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, and 2-3 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

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

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

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

[Formula 17]

In formula (ii-1), R ^c has the same meaning as in formula (ii). R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer greater than or equal to 1; * indicates a bond. The benzene ring in Formula (ii-1) may be further substituted by arbitrary substituents.

(R ^α )

In the formula (ii-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group or an aromatic cyclic group.

Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, Furthermore, 6 or less and 4 or less are preferable normally, and 3 or less are more preferable. For example, 1-6 are preferable, 1-4 are more preferable, 1-3 are still more preferable, and 2-3 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Moreover, carbon number of an alicyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 30 or less are more preferable, 20 or less are still more preferable, 15 The following are particularly preferred. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, 8-15 are especially preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferable from a compatible viewpoint.

On the other hand, although the number of rings which an aromatic cyclic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, 3 or more are more preferable, Moreover, 10 or less and 5 or less are preferable normally. For example, 1-10 are preferable, 1-5 are more preferable, 2-5 are still more preferable, and 3-5 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group is 4 or more normally, 5 or more are preferable, 6 or more are more preferable, 30 or less are preferable, 20 or less are more preferable, and 15 or less are still more preferable. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from a reliability viewpoint.

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

Although n represents an integer of 1 or more, 2 or more are preferable and 3 or less are preferable. For example, 1-3 are preferable and 2-3 are more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

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

As above-mentioned, the benzene ring in Formula (ii-1) may be further substituted by arbitrary substituents. As the 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 not specifically limited, The number may be one, and two or more may be sufficient as them.

From a viewpoint of a patterning characteristic, it is preferable that it is unsubstituted.

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

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

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

[Formula 23]

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

(R ^β )

In the formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group or an aromatic cyclic group.

Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, Moreover, 10 or less and 5 or less are preferable normally. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Moreover, carbon number of an alicyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are still more preferable. For example, 4-40 are preferable, 6-35 are more preferable, 8-30 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Specific examples of the aliphatic ring in the alicyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferable from a compatible viewpoint.

On the other hand, although the number of rings which an aromatic cyclic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, 3 or more are more preferable, Moreover, 10 or less and 5 or less are preferable normally. For example, 1-10 are preferable, 1-5 are more preferable, 2-5 are still more preferable, and 3-5 are still more preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Examples of the aromatic cyclic group include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 10 or more are still more preferable, Furthermore, 40 or less are preferable, 30 or less are more preferable, 20 The following is more preferable, and 15 or less are especially preferable. For example, 4-40 are preferable, 6-30 are more preferable, 8-20 are still more preferable, 10-15 are especially preferable. By using more than the said lower limit, there exists a tendency for image development adhesiveness to become favorable, and there exists a tendency for sclerosis|hardenability to become favorable by using below the said upper limit.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from a reliability viewpoint.

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

Among them, from the viewpoint of compatibility, R ^β is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.

On the other hand, from the viewpoint of reliability, R ^β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

As mentioned above, the benzene ring in Formula (ii-2) may be further substituted by arbitrary substituents. As the 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 not specifically limited, The number may be one, and two or more may be sufficient as them. Moreover, two benzene rings in Formula (ii-2) may be connected through these substituents.

From a viewpoint of a patterning characteristic, it is preferable that it is unsubstituted.

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

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

On the other hand, it is preferable that the partial structure represented by the said Formula (ii) is a partial structure represented by a following formula (ii-3) from a compatible viewpoint.

[Formula 28]

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

The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or anhydride thereof. Further, another OH group is removed, and may be shared with ^{R Z} in another molecule represented by the formula (ii-3), that is, a plurality of formulas (ii-3) are linked through ^{R Z} it may be

Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorend. The 1 type(s) or 2 or more types selected from an acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid are mentioned.

Among these, from the viewpoint of patterning properties, the polybasic acid is preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, More preferably, they are tetrahydrophthalic acid and biphenyl tetracarboxylic acid.

One kind or two or more kinds of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate-based resin (b1-B) may be, for example, R ^X is hydrogen An atom and one in which R ^Z is a polybasic acid residue may be mixed.

The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate-based resin (b1-B) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable. For example, 1-20 are preferable, 1-15 are more preferable, 3-15 are more preferable, 3-10 are still more preferable. Sclerosis|hardenability exists in the tendency for sclerosis|hardenability to become favorable by setting it as more than the said lower limit, and there exists a tendency for image development solubility to become favorable by setting it as below the said upper limit.

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

<(b2) acrylic copolymer resin>

(b2) Although it will not specifically limit if acrylic copolymer resin is an acrylic copolymer resin containing a carboxyl group or a hydroxyl group, It is preferable to have an ethylenically unsaturated group in a side chain. By setting it as having an ethylenically unsaturated group, the film|membrane decrease by an alkali developing solution at the time of image development becomes difficult to occur by photocuring by exposure, and there exists a tendency for surface roughness to become favorable.

(partial structure represented by general formula (I))

(b2) When the acrylic copolymer resin has an ethylenically unsaturated group in the side chain, the partial structure including the side chain having the ethylenically unsaturated group is not particularly limited, but from the viewpoint of easiness of divergence of radicals accompanying the flexibility of the film, For example, it is preferable to have a partial structure represented by the following general formula (I).

[Formula 29]

In formula (I), R<^1> and R<^2> respectively independently represent a hydrogen atom or a methyl group. * indicates a bond hand.)

Moreover, among the partial structures represented by the said Formula (I), the partial structure represented by the following general formula (I') from a viewpoint of a sensitivity or alkali developability is preferable.

[Formula 30]

In formula (I'), R<^1> and R<^2> respectively independently represent a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from the polybasic acid or anhydride thereof. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorend. The 1 type(s) or 2 or more types selected from an acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid are mentioned.

Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and more preferably , tetrahydrophthalic acid, and biphenyltetracarboxylic acid.

(b2) When an acrylic copolymer resin contains the partial structure represented by the said general formula (I), although the content rate is not specifically limited, 10 mol% or more is preferable, 30 mol% or more is more preferable, 50 mol% More preferably, 70 mol% or more is still more preferable, 80 mol% or more is particularly preferable, 98 mol% or less is preferable, and 95 mol% or less is more preferable. For example, 10-98 mol% is preferable, 30-98 mol% is more preferable, 50-98 mol% is still more preferable, 70-98 mol% is still more preferable, 80-95 mol% is more preferable Especially preferred. There exists a tendency for a mechanical characteristic to improve by setting it as more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

(b2) When acrylic copolymer resin contains the partial structure represented by the said general formula (I'), Although the content rate is not specifically limited, 10 mol% or more is preferable, 30 mol% or more is more preferable, 50 mol% or more is more preferable, 70 mol% or more is still more preferable, 80 mol% or more is especially preferable, 98 mol% or less is preferable, and 95 mol% or less is more preferable. For example, 10-98 mol% is preferable, 30-98 mol% is more preferable, 50-98 mol% is still more preferable, 70-98 mol% is still more preferable, 80-95 mol% is more preferable Especially preferred. If it is more than the said lower limit, there exists a tendency for alkali developability and a mechanical characteristic to become favorable easily, Moreover, there exists a tendency for surface roughness to improve and a residue to reduce by setting it as below the said upper limit.

(partial structure represented by general formula (II))

(b2) When an acrylic copolymer resin contains the partial structure represented by the said General formula (I), Although the partial structure contained elsewhere is not specifically limited, From a viewpoint of image development adhesiveness, for example, following General formula (II) It is also preferable to have a partial structure represented by .

[Formula 31]

In said formula (II), R<^3> represents a hydrogen atom or a methyl group, R<^4> represents the alkyl group which may have a substituent, the aromatic ring group which may have a substituent, or the alkenyl group which may have a substituent.

(R ⁴ )

In said Formula (II), R<^4> represents the alkyl group which may have a substituent, the aromatic ring group which may have a substituent, or the alkenyl group which may have a substituent.

Examples ^{of the alkyl group for R 4} include a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 8 or more, more preferably 20 or less, more preferably 18 or less, more preferably 16 or less. It is preferable, 14 or less are still more preferable, and 12 or less are especially preferable. For example, 1-20 are preferable, 1-18 are more preferable, 3-16 are still more preferable, 5-14 are still more preferable, 8-12 are especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, a dicyclopentanyl group or a dodecanyl group is preferable from a developable viewpoint, and a dicyclopentanyl group is more preferable.

Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, methacryl group A loyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples ^{of the aromatic ring group for R 4} include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. 6 or more are preferable, and, as for the carbon number, 24 or less are preferable, 22 or less are more preferable, 20 or less are still more preferable, 18 or less are especially preferable. For example, 6-24 are preferable, 6-22 are more preferable, 6-20 are still more preferable, 6-18 are especially preferable. There exists a tendency for image development adhesiveness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by using below the said upper limit.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring. a ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc. are mentioned.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, Dazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, Thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, A quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. are mentioned. Among these, a benzene ring or a naphthalene ring is preferable from a developable viewpoint, and a benzene ring is more preferable.

In addition, as a substituent which the aromatic ring group may have, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, A carboxyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁴ include a linear, branched or cyclic alkenyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. For example, 2-22 are preferable, 2-20 are more preferable, 2-18 are still more preferable, 2-16 are still more preferable, 2-14 are especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

In addition, as a substituent which the alkenyl group may have, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, A carboxyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

As described above, R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent, among them, an alkyl group or an alkenyl group is preferable from the viewpoint of developability and film strength. , an alkyl group is more preferable.

(b2) When an acrylic copolymer resin contains the partial structure represented by the said General formula (II), Although the content rate is not specifically limited, 0.1 mol% or more is preferable, 0.5 mol% or more is more preferable, 1 mol % or more is more preferable, and 70 mol% or less is preferable, 50 mol% or less is more preferable, 30 mol% or less is still more preferable, and 10 mol% or less is especially preferable. For example, 0.1 to 70 mol% is preferable, 0.1 to 50 mol% is more preferable, 0.5 to 30 mol% is still more preferable, and 1 to 10 mol% is especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

(partial structure represented by general formula (III))

(b2) when the acrylic copolymer resin contains a partial structure represented by the general formula (I), the partial structure represented by the following general formula (III) from the viewpoint of heat resistance and film strength it is preferable

[Formula 32]

In the formula (III), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen An atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group is represented. t represents the integer of 0-5.

(R ⁶ )

In the formula (III), R ⁶ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, A thiol group or the alkyl sulfide group which may have a substituent is represented.

Examples ^{of the alkyl group for R 6} include a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, more preferably 14 or less. More preferably, 12 or less are particularly preferable. For example, 1-20 are preferable, 3-18 are more preferable, 3-16 are still more preferable, 5-14 are still more preferable, 5-12 are especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, a dicyclopentanyl group or a dodecanyl group is preferable from a viewpoint of developability and surface roughness, and a dicyclopentanyl group is more preferable.

Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, methacryl group A loyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁶ include a linear, branched or cyclic alkenyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. For example, 2-22 are preferable, 2-20 are more preferable, 2-18 are still more preferable, 2-16 are still more preferable, 2-14 are especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

In addition, as a substituent which the alkenyl group may have, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, A carboxyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkynyl group for R ⁶ include a linear, branched or cyclic alkynyl group. 2 or more are preferable, and, as for the carbon number, 22 or less are preferable, 20 or less are more preferable, 18 or less are still more preferable, 16 or less are still more preferable, and 14 or less are especially preferable. For example, 2-22 are preferable, 2-20 are more preferable, 2-18 are still more preferable, 2-16 are still more preferable, 2-14 are especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

In addition, as a substituent which the alkynyl group may have, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, A carboxyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

As a halogen atom in R<^6> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Among these, a fluorine atom is preferable from a viewpoint of ink repellency.

Examples ^{of the alkoxy group for R 6} include a linear, branched or cyclic alkoxy group. 1 or more are preferable, and, as for the carbon number, 20 or less are preferable, 18 or less are more preferable, 16 or less are still more preferable, 14 or less are still more preferable, 12 or less are especially preferable. For example, 1-20 are preferable, 1-18 are more preferable, 1-16 are still more preferable, 1-14 are still more preferable, 1-12 are especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

Moreover, as a substituent which the alkoxy group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, methacryl group A loyl group etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkyl sulfide group for R ⁶ include a linear, branched or cyclic alkyl sulfide group. 1 or more are preferable, and, as for the carbon number, 20 or less are preferable, 18 or less are more preferable, 16 or less are still more preferable, 14 or less are still more preferable, 12 or less are especially preferable. For example, 1-20 are preferable, 1-18 are more preferable, 1-16 are still more preferable, 1-14 are still more preferable, 1-12 are especially preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

In addition, as a substituent which the alkyl group in the alkyl sulfide group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, An acryloyl group, a methacryloyl group, etc. are mentioned, From a developable viewpoint, a hydroxyl group and oligoethylene glycol group are preferable.

As such, R ⁶ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or a substituent Although the alkylsulfide group which may have is shown, a hydroxyl group or a carboxyl group is preferable from a developable viewpoint among these, and a carboxyl group is more preferable.

Although t represents the integer of 0-5 in said Formula (III), it is preferable that t is 0 from a viewpoint of synthetic|combination easiness.

(b2) When an acrylic copolymer resin contains the partial structure represented by the said General formula (III), Although the content rate is not specifically limited, 0.5 mol% or more is preferable, 1 mol% or more is more preferable, 2 mol % or more is more preferable. Moreover, 50 mol% or less is preferable, 30 mol% or less is more preferable, 20 mol% or less is still more preferable, and 10 mol% or less is more preferable. For example, 0.5-50 mol% is preferable, 1-30 mol% is more preferable, 1-20 mol% is still more preferable, 2-10 mol% is more preferable. There exists a tendency for surface roughness to improve by using more than the said lower limit, and there exists a tendency for a residue to reduce by setting it as below the said upper limit.

(partial structure represented by general formula (IV))

(b2) When the acrylic copolymer resin has a partial structure represented by the general formula (I), it is also preferable to have a partial structure represented by the following general formula (IV) from the viewpoint of developability as a partial structure to be included.

[Formula 33]

In the formula (IV), R ⁷ represents a hydrogen atom or a methyl group.

(b2) When acrylic copolymer resin contains the partial structure represented by the said General formula (IV), Although the content rate is not specifically limited, 5 mol% or more is preferable, 10 mol% or more is more preferable, 20 mol % or more is more preferable, and 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60 mol% or less is still more preferable. For example, 5-80 mol% is preferable, 10-70 mol% is more preferable, 20-60 mol% is still more preferable. Developability tends to improve by setting it as more than the said lower limit, and there exists a tendency for surface roughness to improve by setting it as below the said upper limit.

On the other hand, (b2) the acid value of the acrylic copolymer resin is not particularly limited, but preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, still more preferably 20 mgKOH/g or more, and , 150 mgKOH/g or less is preferable, 120 mgKOH/g or less is more preferable, 100 mgKOH/g or less is still more preferable, and 50 mgKOH/g or less is still more preferable. For example, 10-150 mgKOH/g is preferable, 10-120 mgKOH/g is more preferable, 15-100 mgKOH/g is still more preferable, 20-50 mgKOH/g is still more preferable. do. Developability tends to improve by setting it as more than the said lower limit, and there exists a tendency for surface roughness to improve by setting it as below the said upper limit.

(b2) Although the weight average molecular weight (Mw) of acrylic copolymer resin is not specifically limited, Usually, 1000 or more, Preferably it is 2000 or more, More preferably, it is 4000 or more, More preferably, it is 6000 or more, More preferably, it is 7000. or more, particularly preferably 8000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, still more preferably 10000 or less. For example, 1000-20000 are preferable, 2000-20000 are more preferable, 4000-15000 are still more preferable, 6000-15000 are still more preferable, 7000-10000 are especially preferable, 8000-10000 are especially preferable. do. Surface roughness tends to improve by using more than the said lower limit, and there exists a tendency for developability to become favorable by setting it as below the said upper limit.

(b2) Although the double bond equivalent of acrylic copolymer resin is not specifically limited, 500 or less are preferable, 400 or less are more preferable, 350 or less are still more preferable, 300 or less are especially preferable, and 100 or more are preferable. , 150 or more are more preferable, 180 or more are still more preferable, and 200 or more are especially preferable. For example, 100-500 are preferable, 150-400 are more preferable, 180-350 are still more preferable, 200-300 are especially preferable. When it is below the said upper limit, there exists a tendency for a mechanical characteristic and surface roughness to improve, and there exists a tendency for storage stability to improve by setting it as more than the said lower limit.

Moreover, as a specific example of (b2) acrylic copolymer resin, resin of Unexamined-Japanese-Patent No. 8-297366 and Unexamined-Japanese-Patent No. 2001-89533 is mentioned, for example.

<(c) Photoinitiator>

(c) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen extraction reaction, and generating polymerization active radicals. You may add and use additives, such as a polymerization accelerator (chain transfer agent) and a sensitizing dye, as needed.

As a photoinitiator, For example, the metallocene compound containing the titanocene compound of Unexamined-Japanese-Patent No. 59-152396 and Unexamined-Japanese-Patent No. 61-151197; Hexaarylbiimidazole derivatives described in Japanese Patent Application Laid-Open No. 2000-56118; N-aryl-α-amino acids and N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Application Laid-Open No. 10-39503 , radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; The oxime ester type compound etc. which are described in Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2006-36750, etc. are mentioned.

As a photoinitiator, a hexaarylbiimidazole compound is especially preferable from a viewpoint of a mechanical property and surface roughness improvement.

As a hexaarylbiimidazole compound, the hexaarylbiimidazole type radical optical radical initiator represented by the following general formula (1-1) and/or the following general formula (1-2) from a viewpoint of a mechanical characteristic is preferable.

[Formula 34]

In the formula, R ¹ to R ³ each independently represent an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, or a halogen atom, l, m and n represents the integer of 0-5 each independently.

The number of carbon atoms of the alkyl group of R ¹ ~ R ³ is is the range of 1-4 is not particularly limited, in terms of mechanical properties, and is preferably 3 or less, more preferably 2 or less. A chain type may be sufficient as an alkyl group, and a cyclic thing may be sufficient as it. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group, and among these, a methyl group and an ethyl group are preferable. R ¹ ~ R to a substituent which may have an alkyl group having from 1 to 4 carbon atoms of ³ are being used in group 1 non-metallic atomic group other than a valence hydrogen, preferred examples include a halogen atom (-F, -Br, -Cl, -I ), a hydroxyl group, and an alkoxy group are mentioned.

In addition, the carbon number of the alkoxy group of R ¹ ~ R ³ is is the range of 1-4 is not particularly limited, in view of the taper angle increases, and is preferably 3 or less, more preferably 2 or less. The alkyl group portion of the alkoxy group may be a chain or a cyclic one. Specific examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group, and among these, a methoxy group and an ethoxy group are preferable. R ¹ ~ R ³ can be the 1-4C-alkoxy groups are also brought substituent is an alkyl group, an alkoxy group which is in the, preferably an alkyl group.

The ^{halogen atom of R 1} to R ³ includes, for example, a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom. Among them, a chlorine atom or a fluorine atom is preferable from the viewpoint of synthesis easiness, and the chlorine atom is more preferably.

In view of these, the sensitivity or ease of synthesis, R ¹ ~ R ³ is more preferably it is preferred, and a chlorine atom in a halogen atom independently.

m, n, and l each independently represent an integer of 0 to 5, but from the viewpoint of synthesis easiness, it is preferable that at least two of m, n and l are an integer of 1 or more, and any two of m, n and l are It is 1, and it is more preferable that the remaining 1 is 0.

As a hexaarylbiimidazole compound represented by general formula (1-1) and/or general formula (1-2), for example, 2,2'-bis(o-chlorophenyl)-4,5,4 ',5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,5,4',5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl) )-4,4',5,5'-tetra (o,p-dichlorophenyl)biimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'- Tetra (o,p-dichlorophenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra (p-fluorophenyl)biimidazole, 2, 2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(o,p-dibromophenyl)biimidazole, 2,2'-bis(o-bromophenyl)- 4,4',5,5'-tetra(o,p-dichlorophenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(p- chloronaphthyl)biimidazole and the like. Among them, hexaphenylbiimidazole compounds are preferable, and those in which the o-position of the benzene ring bonded to the 2,2'-position on the imidazole ring is substituted with a methyl group, a methoxy group, or a halogen atom is more preferable, It is preferable that the benzene ring bonded to the 4,4',5,5'-position on the dazole ring is unsubstituted or substituted with a halogen atom or a methoxy group.

(c) As a photoinitiator, any of the hexaarylbiimidazole compound represented by General formula (1-1) and the hexaarylbiimidazole compound represented by General formula (1-2) may be used, and both may be used together do. When using together, it does not specifically limit about the ratio.

Examples of the titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl), Dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium di ( 2,6-difluorophenyl), dicyclopentadienyl titanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-penta Fluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-difluoro-3- (pyrrol-1-yl) phenyl] and the like.

Further, examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-( 2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4 -oxadiazole, 2-trichloromethyl-5-furyl-1,3,4- oxadiazole, etc. are mentioned.

In addition, as halomethyl-s-triazine derivatives, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl) -4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-e and oxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

In addition, as α-aminoalkylphenone derivatives, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethyl Hexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(di ethylamino) chalcone and the like.

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

[Formula 35]

In the formula (IV), R ^21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.

R ^21b represents an optional substituent including an aromatic ring.

R ^22a represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.

n represents an integer of 0 or 1.

Although ^{the number of carbon atoms of the alkyl group in R 21a} is not particularly limited, from the viewpoint of solubility and sensitivity to a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably usually less than 10. For example, 1-20 are preferable, 1-15 are more preferable, 1-10 are still more preferable, 2-10 are still more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.

Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, or N-acetyl-N -acetoxyamino group etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

^Examples of the aromatic cyclic group for R 21a include an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. Although carbon number of an aromatic ring group is not specifically limited, From a soluble viewpoint with respect to the photosensitive coloring composition, 5 or more are preferable. Moreover, from a developable viewpoint, 30 or less are preferable, 20 or less are more preferable, and 12 or less are still more preferable. For example, 5-30 are preferable, 5-20 are more preferable, 5-12 are still more preferable.

A phenyl group, a naphthyl group, a pyridyl group, a furyl group etc. are mentioned as a specific example of an aromatic ring group, Among these, a phenyl group or a naphthyl group is preferable from a developable viewpoint, and a phenyl group is more preferable.

Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group to which these substituents are linked, and from the viewpoint of developability, an alkyl group, an alkoxy group, group is preferable, and a linked alkoxy group is more preferable.

Among these, from a developable viewpoint, ^{it is preferable that R 21a} is an aromatic ring group which may have a substituent, and it is more preferable that it is an aromatic ring group which has a connected alkoxy group in a substituent.

In addition, R ^21b roneun, preferably there may be mentioned a carbazolyl group, may be optionally tea is oak Santo group or a group which is substituted is substituted diphenyl sulfide that may be substituted. Among these, the carbazolyl group which may be substituted from a viewpoint of a sensitivity is preferable.

In addition, ^{the carbon number of the alkanoyl group in R 22a} is although it does not specifically limit, From a viewpoint of solubility to a solvent and a sensitivity, it is 2 or more normally, Preferably 3 or more, Furthermore, Usually 20 or less, Preferably 15 Below, more preferably, it is 10 or less, More preferably, it is 5 or less. For example, 2-20 are preferable, 2-15 are more preferable, 2-10 are still more preferable, 2-5 are still more preferable, 3-5 are especially preferable. Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.

As a substituent which the alkanoyl group may have, an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Moreover, ^{carbon number of the aryl group in R 22a} is although it does not specifically limit, From a viewpoint of the solubility to a solvent and a sensitivity, it is 7 or more normally, Preferably 8 or more, Furthermore, it is 20 or less normally, Preferably 15. Below, More preferably, it is 12 or less, More preferably, it is 10 or less. For example, 7-20 are preferable, 7-15 are more preferable, 7-12 are still more preferable, 8-12 are still more preferable. Specific examples of the aryl group include a benzoyl group and a naphthoyl group.

As a substituent which the aryl group may have, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, etc. are mentioned, From a viewpoint of synthetic|combination easiness, it is preferable that it is unsubstituted.

Among these, from a viewpoint of a sensitivity ^{, it is preferable that R 22a} is an alkanoyl group which may have a substituent, It is more preferable that it is an unsubstituted alkanoyl group, It is still more preferable that it is an acetyl group.

Moreover, the initiator described in Unexamined-Japanese-Patent No. 2016-133574 is also used preferably from the point that the contamination of the liquid-crystal layer by a coloring agent is reduced.

A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

A sensitizing dye according to the wavelength of an image exposure light source and a polymerization accelerator can be mix|blended with a photoinitiator as needed for the purpose of raising a sensitivity sensitivity. As a sensitizing dye, the xanthene dye described in Unexamined-Japanese-Patent No. 4-221958 and Unexamined-Japanese-Patent No. 4-219756, Unexamined-Japanese-Patent No. 3-239703, Unexamined-Japanese-Patent No. 5-289335. A coumarin dye having a heterocyclic ring as described, a 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. Hei 3-239703 and Hei 5-289335, and a pyromethene dye described in Japanese Patent Application Laid-Open No. Hei 6-19240 , and others, Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52- 112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57- The pigment|dye etc. which have dialkylamino benzene skeleton of Unexamined-Japanese-Patent No. 168088, Unexamined-Japanese-Patent No. 5-107761, Unexamined-Japanese-Patent No. 5-210240, and Unexamined-Japanese-Patent No. 4-288818 are mentioned.

Among these sensitizing dyes, an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzo benzophenone compounds such as phenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p -Dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole , 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p- Diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylamino p-dialkylaminophenyl group-containing compounds, such as phenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine. Among these, 4,4'-dialkylaminobenzophenone is the most preferable.

A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

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

<(d) ethylenically unsaturated compound>

The photosensitive coloring composition of this invention contains (d) an ethylenically unsaturated compound. (d) By including an ethylenically unsaturated compound, a sensitivity improves.

The ethylenically unsaturated compound used for this invention is a compound which has at least 1 ethylenically unsaturated group in a molecule|numerator. Specific examples include (meth)acrylic acid, (meth)acrylic acid alkylester, acrylonitrile, styrene, and monoester of carboxylic acid having one ethylenically unsaturated bond and polyhydric or monohydric alcohol. have.

In this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has 2 or more of ethylenically unsaturated groups in 1 molecule. Although the number of ethylenically unsaturated groups which a polyfunctional ethylenic monomer has is not specifically limited, Usually, it is 2 or more, Preferably it is 4 or more, More preferably, it is 5 or more, More preferably, it is 8 pieces. It is less than, More preferably, it is seven or less. For example, 2-8 pieces are preferable, 4-8 pieces are more preferable, 4-7 pieces are still more preferable, and 5-7 pieces are still more preferable. There exists a tendency to become highly sensitive by setting it as more than the said lower limit, and there exists a tendency for the solubility with respect to a solvent to improve by setting it as below the said upper limit.

As an example of a polyfunctional ethylenic monomer, For example, Ester of an aliphatic polyhydroxy compound and unsaturated carboxylic acid; Ester of aromatic polyhydroxy compound and unsaturated carboxylic acid; The ester etc. obtained by the esterification reaction of polyhydric hydroxy compounds, such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound, and unsaturated carboxylic acid and polybasic carboxylic acid are mentioned.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Acrylic acid of aliphatic polyhydroxy compounds such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Esters, methacrylic acid esters in which acrylates of these exemplary compounds are replaced with methacrylates, itaconic acid esters in the same way as itaconate, crotonic acid esters in place of cronate, maleic acid esters in place of maleate, etc. can be heard

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include aromatic polyacrylates such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. Acrylic acid ester of a hydroxy compound, methacrylic acid ester, etc. are mentioned.

The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyhydric hydroxy compound is not necessarily a single substance, but representative specific examples include a condensate of acrylic acid, phthalic acid, and ethylene glycol, acrylic acid, maleic acid and a condensate of an acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, and a condensate of acrylic acid, adipic acid, butanediol and glycerin.

In addition, examples of the polyfunctional ethylenic monomer used in the present invention include urethane ( meth)acrylates; Epoxy acrylates like the addition reaction product of a polyhydric epoxy compound and hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; Vinyl group-containing compounds, such as divinyl phthalate, etc. are useful.

The urethane (meth) acrylates include, for example, 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 Co., Ltd.), and the like.

Among these, as (d) an ethylenically unsaturated compound from a sclerosis|hardenable viewpoint, it is preferable to use (meth)acrylic-acid alkylester, and it is more preferable to use dipentaerythritol hexaacrylate.

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 the (e) solvent. (e) By including a solvent, a pigment can be disperse|distributed in a solvent, and there exists a tendency for application|coating to become easy.

The photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (c) a photoinitiator, and (d) an ethylenically unsaturated compound, and other compounding components used as needed. , used in a dissolved or dispersed state in a solvent. Among the solvents, an organic solvent is preferable from the viewpoint of dispersibility and applicability.

Among the organic solvents, from the viewpoint of applicability, the organic solvent having a boiling point in the range of 100 to 300°C is preferable, and the organic solvent having a boiling point in the range of 120 to 280°C is more preferable. In addition, the boiling point here means the boiling point in the pressure of 1013.25 hPa, and all are the same about a 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-t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl ether glycol monoalkyl ethers such as oxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether ;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether Acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol mono glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate;

alkyl acetates such as cyclohexanol acetate;

ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, 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, methylhexyl ketones such as ketone, methyl nonyl ketone, and methoxymethyl pentanone;

Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol Ryu ;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane;

alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-methoxypropyl propionate, 3-methyl chain or cyclic esters such as butyl oxypropionate and γ-butyrolactone;

alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

halogenated hydrocarbons such as butyl chloride and amyl chloride;

ether ketones such as methoxymethylpentanone;

nitriles such as acetonitrile and benzonitrile.

Commercially available organic solvents corresponding to the above include Mineral Spirit, Barsol #2, Apco #18 Solvent, Apco Thinner, Socar Solvent No.1 and No.2, Solveso #150, Shell TS28 Solvent, Carr Bitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cellosolve” is a registered trademark; the same hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

These organic solvents may be used independently and may use 2 or more types together.

When forming a colored spacer by the photolithographic method, as an organic solvent, the organic solvent which has a boiling point in the range of 100-200 degreeC is preferable, and the organic solvent which exists in the range of 120-170 degreeC is more preferable.

Among the said organic solvents, the balance of applicability|paintability, surface tension, etc. is favorable, and the point of the solubility of the structural component in a composition is comparatively high, glycol alkyl ether acetates are preferable.

In addition, although glycol alkyl ether acetates may be used independently, they may use other organic solvents together. As an organic solvent to be used together, glycol monoalkyl ethers are particularly preferable. Among them, propylene glycol monomethyl ether is particularly preferred from the viewpoint of solubility of the constituents in the composition. In addition, glycol monoalkyl ethers have high polarity, and when there is too much addition amount, pigments tend to aggregate, and storage stability such as increased viscosity of the photosensitive coloring composition obtained later tends to decrease. Therefore, glycol monoalkyl ethers in a solvent 5 mass % - 30 mass % are preferable, and, as for the ratio, 5 mass % - 20 mass % are more preferable.

Moreover, it is also preferable to use together the organic solvent (Hereinafter, it may call a "high boiling point solvent") which has a boiling point of 150 degreeC or more. By using such a high boiling point solvent together, although a photosensitive coloring composition becomes difficult to dry, it is effective in preventing that the uniform dispersion state of the pigment in a composition is destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation and solidification of the colorant at the tip of the slit nozzle. Among the various solvents mentioned above, especially diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are preferable at the point with such a high effect.

3 mass % - 50 mass % are preferable, as for the content rate of the high boiling point solvent in an organic solvent, 5 mass % - 40 mass % are more preferable, 5 mass % - 30 mass % are especially preferable. By setting it more than the said lower limit, there exists a tendency that it can suppress that a coloring agent etc. precipitate and solidify at the tip of a slit nozzle, for example, and cause a foreign material defect, Moreover, by setting it below the said upper limit, the drying rate of a composition is suppressed from slowing down, There exists a tendency which can suppress problems, such as a tact defect of a reduced pressure drying process, and a pin trace of a prebaking.

In addition, glycol alkyl ether acetates may be sufficient as the high boiling point solvent with a boiling point of 150 degreeC or more, and glycol alkyl ethers may be sufficient as it, In this case, it is not cared about without separately containing the high boiling point solvent of 150 degreeC or more boiling point.

As preferred high boiling point solvents, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3-butylene glycol diacetate , 1,6-hexanol diacetate, triacetin, and the like.

<(f) dispersant>

In the photosensitive coloring composition of this invention, the (f) dispersing agent may be included in order to disperse|distribute (a) a coloring agent finely and to stabilize the dispersed state.

(f) As a dispersing agent, the polymeric dispersing agent which has a functional group is preferable, Moreover, from the point of dispersion stability, a carboxyl group; phosphate group; sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group; quaternary ammonium base; A polymer dispersing agent having a functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is preferable. Among them, a primary, secondary, or tertiary amino group; quaternary ammonium base; A polymer dispersing agent having a basic functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is particularly preferable from the viewpoint of dispersing the pigment with a small amount of the dispersing agent.

Further, as the polymer dispersant, for example, a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, polyoxyethylene di and ester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such a dispersing agent include EFKA (registered trademark, manufactured by BASF, Inc.), DISPERBYK (registered trademark, manufactured by Big Chemi, Inc.), DISPARON (registered trademark, manufactured by Kusumoto Chemicals, Inc.), and SOLSPERSE as a trade name. (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Industries, Ltd.), Polyflo (manufactured by Kyoeisha Chemical), and Azisper (registered trademark, manufactured by Ajinomoto, Ltd.), and the like.

These polymeric dispersants may be used individually by 1 type, or may use 2 or more types together.

The weight average molecular weight (Mw) of a polymer dispersing agent is 700 or more normally, Preferably it is 1000 or more, Moreover, it is 100000 or less normally, Preferably it is 50000 or less. For example, 700-100000 are preferable, 700-50000 are more preferable, and 1000-50000 are still more preferable.

Among them, from the viewpoint of dispersibility of the pigment, (f) the dispersant preferably contains a functional group-containing urethane-based polymer dispersant and/or an acrylic polymer dispersant, and particularly preferably contains an acrylic polymer dispersant.

Moreover, the polymer dispersing agent which has a basic functional group and has a polyester bond and/or a polyether bond from the point of dispersibility and storage property is preferable.

Examples of the urethane-based and acrylic polymer dispersants include DISPERBYK160 to 166 and 182 series (all of which are urethane-based), DISPERBYK2000, 2001, and BYK-LPN21116 (all of which are acrylic) (all of which are manufactured by Bikchemi).

If a chemical structure preferable as a urethane-based polymer dispersant is specifically illustrated, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, and active hydrogen and tertiary in the same molecule and dispersion resins having a weight average molecular weight of 1000 to 200000 obtained by reacting a compound having an amino group, and the like. By treating these with a quaternizing agent such as benzyl chloride, all or a part of the tertiary amino groups can be made into quaternary ammonium base groups.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aliphatic diisocyanates, such as aromatic diisocyanate, such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4' -Methylenebis(cyclohexylisocyanate), ω,ω'-diisocyanate, alicyclic diisocyanate such as dimethylcyclohexane, xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, etc. Aliphatic diisocyanate having a ring, lysine ester triisocyanate, 1,6,11-undecanetriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptane triisocyanate, such as triisocyanate, tris(isocyanatephenylmethane), tris(isocyanatephenyl)thiophosphate, these trimers, water adduct, these polyol adduct, etc. are mentioned. As the polyisocyanate, preferred is a trimer of organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the polyisocyanate is partially formed by using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. After performing trimerization and stopping trimerization by addition of a catalyst poison, solvent extraction and thin film distillation remove unreacted polyisocyanate, The method of obtaining the target isocyanurate group containing polyisocyanate is mentioned can

Examples of compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds having 1 to 25 carbon atoms. alkoxylated with an alkyl group of , and mixtures of two or more thereof.

As polyether glycol, polyether diol, polyether ester diol, and these 2 or more types of mixture are mentioned. Examples of the polyetherdiol include those obtained by copolymerizing an alkylene oxide alone or by copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and A mixture of 2 or more types of them is mentioned.

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

Examples of the polyester glycol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1, 6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2, Aliphatic glycols such as 5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, and xylylene Aromatic glycols such as glycol and bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine) Hexamethylene adipate, polyethylene/propylene adipate, or the like, or polylactonediol or polylactone monool obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

As polycarbonate glycol, poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, etc., as polyolefin glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated poly isoprene glycol etc. are mentioned.

These may be used individually by 1 type, and may use 2 or more types together.

The number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10000 normally, Preferably it is 500-6000, More preferably, it is 1000-4000.

A compound having an active hydrogen and a tertiary amino group in the same 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 a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Atoms are preferred.

Although the tertiary amino group is not specifically limited, For example, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring, a triazole ring, etc. are mentioned.

Examples of such compounds having active hydrogen and tertiary amino groups in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-diamine Propyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N ,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N ,N-dibutyl-1,4-butanediamine; and the like.

In addition, as the nitrogen-containing heterocyclic ring in case the tertiary amino group has a nitrogen-containing heterocyclic structure, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, and a benz Nitrogen-containing hetero 5-membered rings such as imidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring , a nitrogen-containing hetero 6-membered ring, such as an acridine ring and an isoquinoline ring. Preferred among these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

Specific examples of the compounds having these imidazole rings and amino groups include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole and 1-(2-aminoethyl)imidazole. In addition, specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1, 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino -1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, etc. are mentioned. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4 - Triazole is preferred.

These may be used individually by 1 type, and may use 2 or more types together.

A preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound, preferably Preferably it is 20-190 mass parts, More preferably, it is 30-180 mass parts, 0.2-25 mass parts of compounds which have active hydrogen and a tertiary amino group in the same molecule, Preferably it is 0.3-24 mass parts.

The production of the urethane-based polymer dispersant is carried out according to a known method for producing a polyurethane resin. As a solvent at the time of manufacture, usually, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, Esters, such as ethyl acetate, butyl acetate, and cellosolve acetate , hydrocarbons such as benzene, toluene, xylene, and hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol, and tertiary butanol, chlorides such as methylene chloride and chloroform, tetrahydrofuran, diethyl ether, etc. Aprotic polar solvents, such as ethers, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, etc. are used. These may be used individually by 1 type, and may use 2 or more types together.

In the above production, usually, a urethanation reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltindilaurate, dioctyltindilaurate, dibutyltindioctoate, and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; Tertiary amine systems, such as ethylamine and triethylenediamine, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH/g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH/g. The amine value is a value expressed by the number of mg of KOH by titration by neutralizing a basic amino group with an acid and corresponding to the acid value. There exists a tendency for a dispersion capability to become favorable by setting it as more than the said lower limit, and there exists a tendency for it easy to suppress the fall of developability by setting it as below the said upper limit.

In addition, when an isocyanate group remains in the polymer dispersing agent due to the above reaction, further conversion of the isocyanate group to another functional group with an alcohol or an amino compound is preferable because the stability over time of the product increases.

The weight average molecular weight (Mw) of a urethane-type polymer dispersing agent is 1000-20000 normally, Preferably it is 2000-100000, More preferably, it is 3000-50000. There exists a tendency for dispersibility and dispersion stability to become favorable by setting it as more than the said lower limit, and there exists a tendency for it to be easy to suppress the fall of solubility and dispersibility by setting it as below the said upper limit.

Examples of the acrylic polymer dispersant include a random copolymer, a graft copolymer, of an unsaturated group-containing monomer having a functional group (a functional group referred to herein is a functional group described above as a functional group contained in the polymer dispersing agent) and an unsaturated group-containing monomer having no functional group, Preference is given to using block copolymers. These copolymers can be prepared by a known method.

Examples of the unsaturated group-containing monomer having a functional group include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, and 2-(meth)acryloyloxyethylhexa Unsaturated monomers having a carboxyl group such as hydrophthalic acid and acrylic acid dimer; can be mentioned as specific examples. 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, iso Butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone , styrene and its derivatives, N-substituted maleimides such as α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide, acrylonitrile, vinyl acetate, and polymethyl (meth)acryl Macromonomers, such as a late macromonomer, a polystyrene macromonomer, a poly 2-hydroxyethyl (meth)acrylate macromonomer, a polyethyleneglycol macromonomer, a polypropylene glycol macromonomer, and a polycaprolactone macromonomer, etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.

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

Although the B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the functional group, one B block may contain a partial structure derived from two or more types of monomers, and these are random copolymerized in the B block. Or you may contain in any aspect of block copolymerization.

The A-B or B-A-B block copolymer is prepared, for example, by the living polymerization method shown below.

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Among these, the anionic living polymerization method is a polymerization active species an anion, and is shown, for example, by the following scheme.

[Formula 36]

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

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

[Formula 37]

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

When synthesizing this acrylic polymer dispersant, Japanese Patent Application Laid-Open No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Ute, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Proceedings of Polymers, 46, 189 (1989) , M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), etc. are adopted. can do.

The acrylic polymer dispersant usable in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block/B block ratio constituting the copolymer is 1/99 to 80/20, particularly 5/95 to It is preferable that it is 60/40 (mass ratio), and there exists a tendency which can ensure the balance of dispersibility and storage stability by setting it as this range.

In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol, and good dispersibility can be ensured by setting it within this range. tends to be

In addition, in such a block copolymer, an amino group generated during the production process is usually contained in some cases, and the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, further preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably is 75 mgKOH/g or less. For example, 10-90 mgKOH/g is preferable, 30-80 mgKOH/g is more preferable, 50-75 mgKOH/g is still more preferable.

Here, the amine titer of the dispersing agent such as these block copolymers is expressed by the amount of the base per 1 g of the solid content excluding the solvent in the dispersant sample and the mass of the equivalent KOH, and is measured by the following method.

In a 100 ml beaker, 0.5 to 1.5 g of the dispersant sample is precisely weighed and dissolved with 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated _{with a 0.1 mol/L HClO 4 acetic acid solution.} Using the inflection point of the titration pH curve as the titration end point, the amine number is calculated by the following formula.

Amine number [mgKOH/g] = (561 × V)/(W × S)

[However, W: Weighing amount of dispersant sample [g], V: titration amount [ml] at the end point of titration, S: shows the solid content concentration [mass %] of the dispersant sample.]

In addition, although the acid value of this block copolymer differs depending on the presence or absence and type of the acidic group which becomes the origin of the acid value, it is generally preferable that it is low, and is usually 10 mgKOH/g or less, and its weight average molecular weight ( Mw) has a preferable range of 1000 to 100000. There exists a tendency for favorable dispersibility to be securable by setting it as the said range.

When the acrylic polymer dispersant has a quaternary ammonium base as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter, “repeating unit (i)”) It is preferable to have ).

[Formula 38]

In the formula (i), R ³¹ to R ³³ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ³¹ to R ³³ Two or more of them may combine with 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 formula (i) The number of carbon atoms of R ³¹ ~, the alkyl group which may have a substituent in R ³³ is not particularly limited, but is usually not less than 1, and more preferably not more than desirable, and 610 or less. For example, 1-10 are preferable and 1-6 are more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or it is preferable that it is a hexyl group, and it is more preferable that they are a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either linear or branched chain type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexyl methyl group, may also be included.

The number of carbon atoms of an aryl group which may, have a substituent at the R ³¹ ~ R ³³ in the formula (i) is not particularly limited, but is usually 6 or more and less than 16, it is preferable, and more preferably 12 or less . For example, 6-16 are preferable and 6-12 are more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among them, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di It is preferable that it is an ethylphenyl group, and it is more preferable that they are a phenyl group, a methylphenyl group, or an ethylphenyl group.

The formula (i) The number of carbon atoms of R ³¹ ~ of the aralkyl group, which may have a substituent in R ³³ is not particularly limited, but is usually not less than 7, and, less than 16, it is preferable, and more preferably 12 or less . For example, 7-16 are preferable and 7-12 are more preferable. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, and among these, a phenylmethyl group, a phenylethyl group, and a phenyl group A propyl group or a phenylbutyl group is preferable, and it is more preferable that it is a phenylmethyl group or a phenylethyl group.

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

Moreover, when the said acrylic polymer dispersing agent has a tertiary amine as a functional group, from a dispersibility viewpoint, it is preferable to have a repeating unit represented by following formula (ii) (Hereinafter, it may be referred to as "repeating unit (ii)"). do.

[Formula 39]

In the 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 These may combine with each other to form a cyclic structure. R ³⁷ is a hydrogen atom or a methyl group. Z is a divalent linking group.

Further, the alkyl group which may have substituents in the R ³⁵ and R ³⁶ in the formula (ii), can be preferably employed as one example R ³¹ ~ R ³³ in the formula (i).

Similarly, as the aryl group which may have a substituent in ^{R 35} and R ³⁶ in the formula (ii) ^{, those exemplified as R 31} to R ^{33 in} the formula (i) can be preferably employed. Further, the aralkyl group which may, have a substituent in R ³⁵ and R ³⁶ in the formula (ii), can be preferably employed as one example R ³¹ ~ R ³³ in the formula (i).

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

As substituents the above formula optionally (i) R ³¹ ~ R ³³ and the formula (ii) R ³⁵ and R ³⁶ has groups are an alkyl group, an aralkyl group or an aryl group in the a is a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like.

In the formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ⁴³ - group, and -COOR. ⁴⁴ - group [provided that R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)], preferably -COOR ⁴⁴ - It's gi.

In the 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.

Although the content rate of the repeating unit represented by said formula (i) is not specifically limited, From a dispersibility viewpoint, the sum of the content rate of the repeating unit represented by said formula (i) and the content rate of said repeating unit represented by said formula (ii) It is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and preferably 5 mol% or more. and more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.

In addition, the content ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, preferably 1 mol% or more, more preferably 5 mol% or more, 10 mol% or more is still more preferable, 50 mol% or less is preferable, 30 mol% or less is more preferable, 20 mol% or less is still more preferable, 15 mol% or less is especially preferable. For example, 1-50 mol% is preferable, 5-30 mol% is more preferable, 5-20 mol% is still more preferable, 10-15 mol% is especially preferable.

In addition, the content ratio of the repeating unit represented by the above formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, preferably 5 mol% or more, more preferably 10 mol% or more, 15 mol% or more is more preferable, 20 mol% or more is particularly preferable, and 60 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is still more preferable, 25 mol% or less is particularly preferred. For example, 5-60 mol% is preferable, 10-40 mol% is more preferable, 15-30 mol% is still more preferable, 20-25 mol% is especially preferable.

In addition, the polymer dispersant is a repeating unit represented by the following formula (iii) from the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability (hereinafter referred to as "repeating unit (iii)" in some cases. ) is preferred.

[Formula 40]

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

^{Although carbon number of the alkyl group which may have a substituent in R 41} of said Formula (iii) is not specifically limited, Usually, 1 or more, 2 or more are preferable, Moreover, 10 or less are preferable, 6 or less are more desirable. For example, 1-10 are preferable, 1-6 are more preferable, and 2-6 are still more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or it is preferable that it is a hexyl group, and it is more preferable that they are a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either linear or branched chain type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

Further, n in the formula (iii) is preferably 1 or more, more preferably 2 or more, more preferably 10 or less, and more desirable. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable.

In addition, the content rate of the repeating unit represented by the said Formula (iii) in all the repeating units of a polymer dispersing agent is although it does not specifically limit, 1 mol% or more is preferable, 2 mol% or more is more preferable, 4 mol% or more More preferably, 30 mol% or less is preferable, 20 mol% or less is more preferable, and 10 mol% or less is still more preferable. For example, 1-30 mol% is preferable, 2-20 mol% is more preferable, 4-10 mol% is still more preferable. When it is in the said range, there exists a tendency for compatibility with respect to binder components, such as a solvent, and coexistence of dispersion stability to become possible.

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

[Formula 41]

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

^{Although the number of carbon atoms of the alkyl group which may have a substituent in R 38} in the formula (iv) is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 4 or more, and 10 or less. It is preferable, and it is more preferable that it is 8 or less. For example, 1-10 are preferable, 1-8 are more preferable, 2-8 are still more preferable, 4-8 are still more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or it is preferable that it is a hexyl group, and it is more preferable that they are a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either linear or branched chain type may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

^{Although carbon number of the aryl group which may have a substituent in R 38} of said Formula (iv) is not specifically limited, Usually, 6 or more, and 16 or less are preferable, 12 or less are more preferable, 8 or less is more preferable. For example, 6-16 are preferable, 6-12 are more preferable, and 6-8 are still more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among them, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di It is preferable that it is an ethylphenyl group, and it is more preferable that they are a phenyl group, a methylphenyl group, or an ethylphenyl group.

^{Although the number of carbon atoms of the aralkyl group which may have a substituent in R 38} in the formula (iv) is not particularly limited, it is usually 7 or more, and preferably 16 or less, more preferably 12 or less, and 10 or less. more preferably. For example, 7-16 are preferable, 7-12 are more preferable, 7-10 are still more preferable. Specific examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among them, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenylbutyl group is It is preferable, and it is more preferable that it is a phenylmethyl group or a phenylethyl group.

Among these, from a viewpoint of solvent compatibility and dispersion stability ^{, it is preferable that R 38} is an alkyl group or an aralkyl group, and it is more preferable that it is a methyl group, an ethyl group, or a phenylmethyl group.

As ^{a substituent which the alkyl group in R 38} may have, a halogen atom, an alkoxy group, etc. are mentioned. Moreover, as a substituent which the aryl group or aralkyl group may have, a chain|strand-type alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. In addition, the ^{linear alkyl group represented by R 38} includes both linear and branched chain types.

Further, the content ratio of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol% or more from the viewpoint of dispersibility. This is more preferable, and 80 mol% or less is preferable, and 70 mol% or less is more preferable. For example, 30-80 mol% is preferable, 40-80 mol% is more preferable, 50-70 mol% is still more preferable.

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

A polymer dispersing agent is a block having an A block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and a repeating unit (ii) from the viewpoint of further improving the dispersibility. It is preferable that it is a copolymer. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, unexpectedly, the dispersing ability of the dispersant 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).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any aspect of random copolymerization or block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may each contain 2 or more types in one A block, In that case, each repeating unit is either random copolymerization or block copolymerization in the A block. You may contain it in an aspect.

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 repeating units derived from the above-mentioned (meth)acrylic acid ester monomer. can The content of the repeating units other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are in the A block It is most preferable not to contain it.

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

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

<Other compounding components of the photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, in addition to the above components, adhesion improvers such as silane coupling agents, surfactants (applicability improvers), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, development improving agents, Additives, such as a ultraviolet absorber and antioxidant, can be mix|blended suitably.

(1) Adhesion improver

In the photosensitive coloring composition of this invention, in order to improve adhesiveness with a board|substrate, you may contain an adhesiveness improving agent. As a close_contact|adherence improving agent, a silane coupling agent, a phosphoric acid group containing compound, etc. are preferable.

As a kind of a silane coupling agent, various things, such as an epoxy type, a (meth)acrylic type, and an amino type, can be used individually by 1 type or in mixture of 2 or more types.

As a preferable silane coupling agent, For example, (meth)acryloxysilanes, such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyl trimethoxysilane, 2-(3,4-epoxycyclo Epoxysilanes such as hexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, 3-ureido Although ureidosilanes, such as propyltriethoxysilane, and isocyanate silanes, such as 3-isocyanate propyltriethoxysilane, are mentioned, Especially preferably, it is the silane coupling agent of epoxysilanes.

As a phosphoric acid group containing compound, (meth)acryloyl group containing phosphates are preferable, and what is represented by the following general formula (g1), (g2) or (g3) is preferable.

[Formula 42]

In the formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are an integer of 1 to 10, and m is 1, 2 or 3.

These phosphoric acid group containing compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

(2) surfactant

You may make the photosensitive coloring composition of this invention contain surfactant for an applicability|paintability improvement.

As surfactant, various things, such as an anionic, cationic, nonionic, amphoteric surfactant, can be used, for example. Among them, it is preferable to use a nonionic surfactant from the viewpoint of having a low possibility of adversely affecting various properties, and among them, a fluorine-based surfactant or a silicone-based surfactant is effective in terms of applicability.

As such surfactant, TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos Corporation), BYK-300, BYK-325, BYK-330 (manufactured by Bikchemi), KP340 (manufactured by Shin-Etsu Silicone), Megapac (registered trademark, hereinafter the same) F-470, Megapac F-475, Megapac F-478, Megapac F-554, Megapac F-559 (manufactured by DIC), SH7PA (made by Toray Dow Corning), DS-401 (made by Daikin), L-77 (made by Nippon Unika), FC4430 (made by 3M), etc. are mentioned.

In addition, surfactant may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(3) pigment derivatives

You may make the photosensitive coloring composition of this invention contain a pigment derivative as a dispersing auxiliary agent in order to improve dispersibility and storage stability.

Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Although derivatives, such as a pyrrole type and a dioxazine type, are mentioned, Especially, a phthalocyanine type and a quinophthalone type are preferable.

As a substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are directly attached to the pigment skeleton or an alkyl group, an aryl group, a heterocyclic group, etc. and those bonded via a sulfonic acid group. In addition, two or more of these substituents may be substituted by one pigment frame|skeleton.

Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, dioxazine sulfonic acid derivatives, and the like. . These may be used individually by 1 type, and may use 2 or more types together.

(4) photoacid generators

A photo-acid generator is a compound which can generate|occur|produce an acid by ultraviolet-ray, and a crosslinking reaction advances by the action of the acid which generate|occur|produces when it exposes, for example, when crosslinking agents, such as a melamine compound, exist. Among these photo-acid generators, those having high solubility in solvents, particularly solvents used for the photosensitive coloring composition, are preferable, for example, diphenyliodonium, ditolyliodonium, and phenyl(p-anisyl)iodine. nium, bis(m-nitrophenyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p-chlorophenyl)iodonium, bis(n-dodecyl)iodonium, p-isobutylphenyl ( Chloride, bromide, or borofluoride salt of diaryliodonium, such as p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium, such as triphenylsulfonium, hexafluorophosphate salts, hexafluoroarsenate salts, aromatic sulfonates, tetrakis(pentafluorophenyl)borate salts, and sulfonium organoboron complexes such as diphenylphenacylsulfonium(n-butyl)triphenylborate; or and triazine compounds such as 2-methyl-4,6-bistrichloromethyltriazine and 2-(4-methoxyphenyl)-4,6-bistrichloromethyltriazine, but is not limited thereto. .

(5) crosslinking agent

A crosslinking agent can further be added to the photosensitive coloring composition of this invention, For example, a melamine or a guanamine type compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (6).

[Formula 43]

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 , R ⁶⁶ and when one of R ⁶⁷ represents a CH ₂ OR ⁶⁸ group and R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group, and R ⁶² , The remainder of R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent hydrogen or a -CH ₂ OR ⁶⁸ group, and R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Here, the C6-C12 aryl group is typically a phenyl group, 1-naphthyl group, or 2-naphthyl group, Substituents, such as an alkyl group, an alkoxy group, and a halogen atom, may couple|bond with these phenyl group or a naphthyl group. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

In the melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1), hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethyl melamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine, and the like.

[Formula 44]

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 is -CH ₂ OR ⁶⁸ , and ^{the remainder of R 62} , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ , independently of each other, represent a hydrogen atom or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or an alkyl group.

In addition, in the guanamine-type compound corresponded to General formula (6), ie, R<^61> in General formula (6) is aryl, tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzo guanamine, tetraethoxymethylbenzoguanamine, and the like.

In addition, a crosslinking agent having a methylol group or a methylol alkyl ether group may be used. An example is given below.

2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl)perhydro -1,3,5-triazin-2-one (common name N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethyleneurea or its dimethyl ether, 3,5-bis(hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (commonly known as dimethyloluron) or its dimethyl ether, tetramethylolglyoxaldiolein, or its tetramethylether.

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

(6) mercapto compounds

As a polymerization accelerator, it is also possible to add a mercapto compound in order to improve the curability of the surface of the cured product and to improve the surface roughness.

Examples of the mercapto compound include a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound.

As the mercapto group-containing compound having an aromatic ring, a compound represented by the following general formula (1-3) is preferably used from the viewpoint of photocurability.

[Formula 45]

In formula (1-3), Z represents -O-, -S- or -NH-, and R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ each independently represent a hydrogen atom or a monovalent substituent.

Among these, -S- or -NH- is preferable from a viewpoint of photocurability, and -NH- is more preferable.

Further, from the viewpoint of photocurability, R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom. .

Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H )-quinazoline, β-mercaptonaphthalene, and a mercapto group-containing compound having an aromatic ring such as 1,4-dimethyl mercaptobenzene, from the viewpoint of a taper angle, 2-mercaptobenzothiazole, 2 - Mercaptobenzoimidazole is preferred.

On the other hand, as the aliphatic mercapto group-containing compound, hexanedithiol, decanedithiol, or a compound represented by the following general formula (1-4) is preferably used from the viewpoint of photocurability.

[Formula 46]

In formula (1-4), m represents the integer of 0-4, and n represents the integer of 2-4. R ⁷¹ and R ⁷² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents an n-valent group.

In the said General formula (1-4), it is preferable that m is 1 or 2 from a viewpoint of photocurability. Moreover, from a viewpoint of photocurability, it is preferable that n is 3 or 4, and 4 is more preferable.

Further, the alkyl group of R ⁷¹ and R ⁷² are, from the point of view of the photo-curable, preferably containing 1 to 3 carbon atoms. From the viewpoint of photocurability, ^{at least one of R 71} and R ⁷² , for example, R ⁷² is preferably a hydrogen atom, and in this case, R ⁷¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. .

When n is 2, from a viewpoint of photocurability, X is a C1-C6 alkylene group which may have an ether bond and/or a branched part is preferable. From a photocurable viewpoint, a C1-C6 alkylene group is more preferable especially, and a C4 alkylene group is still more preferable.

When n is 3, it is preferable from a viewpoint of photocurability that X is a structure represented by the following general formula (1-5) or (1-6).

[Formula 47]

In formula (1-5), R ⁷³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methylol group. Among R ⁷³ , an ethyl group is preferable from the viewpoint of photocurability.

[Formula 48]

In formula (1-6), R ⁷⁴ represents a C1-C4 alkylene group. Among R ⁷⁴ , an ethylene group is preferable from the viewpoint of photocurability.

On the other hand, when n is 4, it is preferable that X is a structure represented by the following general formula (1-7).

[Formula 49]

Specifically, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylol propane tris (3-mer) Captopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropio) nate), butanediol bis (3-mercapto butyrate), ethylene glycol bis (3-mercapto butyrate), trimethylolpropane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto butyrate), penta Erythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)- Trion etc. are mentioned.

Among them, trimethylol propane tris (3-mercapto propionate), pentaerythritol tetrakis (3-mercapto propionate), pentaerythritol tris (3-mercapto propionate), and trimethylol propane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferable, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3 -mercaptobutyrate) is more preferable.

These can use various things individually by 1 type or in mixture of 2 or more types.

Among these, from the viewpoint of photocurability, at least one selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, and 2-mercaptobenzooxazole, and a photopolymerization initiator are combined, photopolymerization It is preferably used as an initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzoimidazole may be used, and 2-mercaptobenzothiazole and 2-mercaptobenzoimidazole may be used together and may be used.

In addition, it is preferable to use at least one selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) from the viewpoint of photocurability.

Moreover, it is preferable to use together the mercapto group containing compound which has an aromatic ring, and the mercapto group containing compound of an aliphatic type, especially from a viewpoint of photocurability. This is because, by using a mask with a narrow opening, the illuminance per unit area is lowered by diffraction during exposure, and it is more susceptible to oxygen inhibition than in the case where the line width is large, and the surface hardenability tends to be lowered.

In particular, when a hexaarylbiimidazole-based photopolymerization initiator is used as the photopolymerization initiator (c), it is preferable to use a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound in combination. On the other hand, when an acetophenone-based photopolymerization initiator is used, there is a tendency that the effect can be sufficiently obtained even with single use of an aliphatic mercapto group-containing compound.

For example, at least one selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, and 2-mercaptobenzooxazole, and pentaerythritol tetrakis (3-mercaptopropionate) It is preferable to use in combination with at least one selected from the group consisting of , pentaerythritol tetrakis (3-mercaptobutyrate) and a photopolymerization initiator.

(7) polymerization inhibitor

You may contain a polymerization inhibitor from a viewpoint of shape control.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferable. In addition, from the viewpoint of safety to the human body, hydroquinone monomethyl ether and methyl hydroquinone are preferable.

A polymerization inhibitor may contain 1 type or 2 or more types. (b) When manufacturing alkali-soluble resin, a polymerization inhibitor may be contained in the said resin, you may use it as a polymerization inhibitor of this invention, and other than a polymerization inhibitor, polymerization inhibitor same or different from it in resin. You may add an agent at the time of photosensitive coloring composition manufacture.

<Ingredient compounding quantity in photosensitive coloring composition>

The photosensitive coloring composition of this invention WHEREIN: Although the content rate of (b) alkali-soluble resin is not specifically limited, Usually 5 mass % or more in total solid, Preferably it is 10 mass % or more, More preferably, it is 15 mass % or more. , more preferably 20 mass% or more, particularly preferably 25 mass% or more, and usually 80 mass% or less, preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less. % or less, still more preferably 40 mass% or less, and particularly preferably 35 mass% or less. For example, 5-80 mass % is preferable, 5-70 mass % is more preferable, 10-60 mass % is still more preferable, 15-50 mass % is still more preferable, 20-40 mass % is more preferable It is especially preferable, and 25-35 mass % is especially preferable. (b) By making the content rate of alkali-soluble resin more than the said lower limit, there exists a tendency for image development solubility to improve. Moreover, there exists a tendency for a mechanical characteristic to improve by using below the said upper limit.

(c) Although the content rate of a photoinitiator is not specifically limited, Usually 0.1 mass % or more in total solid, Preferably it is 0.5 mass % or more, More preferably, it is 1 mass % or more, More preferably, it is 1.5 mass % or more. , usually 15 mass% or less, preferably 10 mass% or less, more preferably 8 mass% or less, still more preferably 6 mass% or less, particularly preferably 4 mass% or less. For example, 0.1-15 mass % is preferable, 0.1-10 mass % is more preferable, 0.5-8 mass % is still more preferable, 1-6 mass % is especially preferable, 1.5-4 mass % is especially desirable. (c) By making the content rate of a photoinitiator more than the said lower limit, there exists a tendency for photocurability to become high, and for surface roughness to improve, and for it to exist in the tendency for developing solubility to improve by setting it as below the said upper limit.

(c) When using a polymerization accelerator together with a photoinitiator, the content rate of a polymerization accelerator is in the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.05 mass % or more, Usually 10 mass % or less, Preferably is 5 mass % or less, for example, 0.05-10 mass %, Preferably it is 0.05-5 mass %. Moreover, a polymerization accelerator is 0.1-50 mass parts normally with respect to 100 mass parts of (c) photoinitiators, Preferably it is used in the ratio of 0.1-20 mass parts. When the content ratio of the polymerization accelerator is higher than or equal to the lower limit, a decrease in sensitivity to exposure light tends to be suppressed. tend to be restrained.

Moreover, (c) When using a sensitizing dye with a photoinitiator, the content rate of a sensitizing dye is in the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.1 mass % or more, More preferably, 0.2 mass %. More preferably, it is 0.3 mass % or more, More preferably, it is 5 mass % or less, More preferably, it is 4 mass % or less, More preferably, it is 3 mass % or less. For example, 0.1-5 mass % is preferable, 0.2-4 mass % is more preferable, 0.3-3 mass % is still more preferable. By using more than the said lower limit, there exists a tendency for photocurability to become high and surface roughness to improve, and also by setting it as below the said upper limit, there exists a tendency for image development solubility to improve.

(d) The content rate of an ethylenically unsaturated compound is 1 mass % or more normally in the total solid of the photosensitive coloring composition of this invention, Preferably it is 5 mass % or more, More preferably, it is 10 mass % or more, More preferably is 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more, and is usually 80% by mass or less, preferably 70% by mass or more. Hereinafter, more preferably, it is 65 mass % or less. For example, 1-80 mass % is preferable, 5-80 mass % is more preferable, 10-70 mass % is still more preferable, 20-70 mass % is still more preferable, 30-70 mass % is more preferable It is especially preferable, 40-65 mass % is especially preferable, and 50-65 mass % is the most preferable. (d) By making the content rate of an ethylenically unsaturated compound more than the said lower limit, there exists a tendency for a mechanical characteristic to improve, Moreover, there exists a tendency for image development solubility to improve by using below the said upper limit.

On the other hand, the content rate of (b) alkali-soluble resin with respect to 100 mass parts of (d) ethylenically unsaturated compounds is although it does not specifically limit, 10 mass parts or more are preferable, 20 mass parts or more are more preferable, 30 mass parts More preferably, 40 parts by mass or more is particularly preferable, and usually 150 parts by mass or less and 120 parts by mass or less are preferable, more preferably 100 parts by mass or less, and still more preferably 70 parts by mass or less. For example, 10-150 mass parts is preferable, 20-120 mass parts is more preferable, 30-100 mass parts is still more preferable, 40-70 mass parts is especially preferable. By using more than the said lower limit, there exists a tendency for developing solubility to improve, and there exists a tendency for a mechanical characteristic to become favorable by setting it as below the said upper limit.

Moreover, in the photosensitive coloring composition of this invention, the content rate of the total solid is 5 mass % or more normally by using (e) a solvent, Preferably it is 10 mass % or more, More preferably, 15 mass % or more, and Usually, it is 50 mass % or less, Preferably it is 30 mass % or less, It is crude so that it may become 25 mass % or less more preferably. For example, 5-50 mass % is preferable, 10-30 mass % is more preferable, 15-25 mass % is still more preferable.

When the photosensitive coloring composition of this invention contains (f) a dispersing agent, the content rate of (f) dispersing agent is 0.5 mass % or more normally in the total solid of the photosensitive coloring composition, 1 mass % or more is preferable, 1.5 mass % The above is more preferable, and usually 30 mass % or less and 20 mass % or less are preferable, 15 mass % or less is more preferable, 10 mass % or less is still more preferable, and 5 mass % or less is especially preferable. For example, 0.5-30 mass % is preferable, 0.5-20 mass % is more preferable, 1-15 mass % is still more preferable, 1-10 mass % is still more preferable, 1.5-5 mass % is more preferable Especially preferred. (f) By making the content rate of a dispersing agent more than the said lower limit, there exists a tendency for storage stability to improve, and there exists a tendency for display reliability to improve by using below the said upper limit.

Moreover, as for the content rate of (f) dispersing agent with respect to 100 mass parts of (a) coloring agents, 5 mass parts or more and 10 mass parts or more are more preferable normally, 20 mass parts or more are still more preferable, Usually 50 mass parts. Hereinafter, it is especially preferable that it is 40 mass parts or less. For example, 5-50 mass parts is preferable, 10-50 mass parts is more preferable, 20-40 mass parts is still more preferable. (f) By making the content rate of a dispersing agent more than the said lower limit, there exists a tendency for storage stability to improve, and there exists a tendency for display reliability to improve by using below the said upper limit.

When using an adhesion improving agent, the content rate is 0.1 mass % or more normally in the total solid of the photosensitive coloring composition, 0.2 mass % or more is preferable, 0.5 mass % or more is more preferable, and 30 mass % normally Hereinafter, 20 mass % or less is preferable, 10 mass % or less is more preferable, 5 mass % or less is still more preferable, 3 mass % or less is especially preferable. For example, 0.1-30 mass % is preferable, 0.2-20 mass % is more preferable, 0.2-10 mass % is still more preferable, 0.5-5 mass % is still more preferable, 0.5-3 mass % is Especially preferred. By making the content rate of an adhesion improver more than the said lower limit, there exists a tendency for adhesiveness to improve, and there exists a tendency for a residue to reduce by using below the said upper limit.

Moreover, when using surfactant, the content rate is 0.001-10 mass % normally in the total solid of the photosensitive coloring composition, Preferably it is 0.005-1 mass %, More preferably, 0.01-0.5 mass % is the most preferable. Preferably, it is 0.03-0.3 mass %. When the content ratio of the surfactant is more than the lower limit, the smoothness and uniformity of the coating film tend to be easily expressed, and when the content ratio of the surfactant is less than the upper limit, the smoothness and uniformity of the coating film are easily expressed, and deterioration of other properties can also be suppressed. tends to

When using a mercapto compound, the content rate is 0.1 mass % or more normally in the total solid of the photosensitive coloring composition, 0.2 mass % or more is preferable, 0.5 mass % or more is more preferable, and 30 mass % or more normally. Mass % or less and 20 mass % or less are preferable, 10 mass % or less is more preferable, 5 mass % or less is still more preferable, 3 mass % or less is especially preferable. For example, 0.1-30 mass % is preferable, 0.2-20 mass % is more preferable, 0.2-10 mass % is still more preferable, 0.5-5 mass % is still more preferable, 0.5-3 mass % is Especially preferred. By making the content rate of a mercapto compound more than the said lower limit, there exists a tendency for photocurability to become high, and for surface roughness to improve, and by setting it as below the said upper limit, there exists a tendency for storage stability to improve.

When using a polymerization inhibitor, the content rate is 0.05 mass % or more normally in the total solid of the photosensitive coloring composition, 0.1 mass % or more is preferable, 0.2 mass % or more is more preferable, and 2 Mass % or less and 1 mass % or less are preferable, 0.8 mass % or less is more preferable, 0.7 mass % or less is still more preferable, and 0.5 mass % or less is especially preferable. For example, 0.05-2 mass % is preferable, 0.05-1 mass % is more preferable, 0.1-0.8 mass % is still more preferable, 0.1-0.7 mass % is still more preferable, 0.2-0.5 mass % is Especially preferred. By making the content rate of a polymerization inhibitor more than the said lower limit, there exists a tendency for resolution to become high, and there exists a tendency for sclerosis|hardenability to become high by using below the said upper limit.

<Physical properties of the photosensitive coloring composition>

The photosensitive coloring composition of this invention can be used suitably for the object for colored spacer formation, From a viewpoint of using as a colored spacer, it is preferable that the optical density (OD) per 1 micrometer of film thickness of the coating film is high. As a single colored spacer obtained by hardening|curing the photosensitive coloring composition of this invention, it is preferable that it is 0.1 or more, It is more preferable that it is 0.15 or more, It is still more preferable that it is 0.2 or more, It is still more preferable that it is 0.25 or more. Here, the optical density (OD) is a value measured by the method mentioned later.

<The manufacturing method of the photosensitive coloring composition>

The photosensitive coloring composition of this invention is manufactured according to a conventional method.

In general, (a) the colorant is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (a) colorant is finely divided by the dispersion treatment, the coating properties of the photosensitive coloring composition are improved.

Dispersion treatment is preferably carried out in a system in which (a) a colorant, (e) a solvent, and (f) a dispersant, and optionally (b) some or all of the alkali-soluble resin are used in combination (hereinafter, dispersion treatment). The mixture to be provided in the above and the composition obtained by the treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular (f), when a polymer dispersing agent is used as the dispersing agent, it is preferable because the time-dependent thickening of the obtained ink and photosensitive coloring composition is suppressed (excellent in dispersion stability).

Thus, in the process of manufacturing a photosensitive coloring composition, it is preferable to manufacture the pigment dispersion liquid containing at least (a) a coloring agent, (e) a solvent, and (f) a dispersing agent. As (a) coloring agent, (e) solvent, and (f) dispersing agent which can be used for a pigment dispersion liquid, what was described as what can be used for the photosensitive coloring composition, respectively can be employ|adopted preferably.

Moreover, when a dispersion process is performed with respect to the liquid containing all the components mix|blended with the photosensitive coloring composition, the highly reactive component may be modified|denatured by the heat|fever generated at the time of a dispersion process. Therefore, it is preferable to perform a dispersion process with the system which does not contain (c) a photoinitiator or (d) an ethylenically unsaturated compound.

When the (a) colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment condition is that the temperature is usually 0°C to 100°C, preferably in the range of room temperature to 80°C. The dispersion time tends to vary depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like, and may be appropriately adjusted. 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 or the photosensitive coloring composition is applied to the substrate is in the range of 50 to 300. By setting it as more than the said lower limit, the dispersion process is not enough, and residual|survival of coarse pigment ((a) coloring agent) particle|grains can be suppressed, and there exists a tendency for developability, adhesiveness, resolution, etc. to be easy to make sufficient thing. Moreover, by setting it below the said upper limit, it can suppress that a pigment is crushed and generation|occurrence|production of many ultrafine particles can be suppressed, and there exists a tendency for dispersion stability to be made favorable.

In addition, the dispersed particle diameter of the pigment disperse|distributed in ink is 0.03-0.3 micrometer normally, and it is measured by the dynamic light scattering method etc.

Next, the ink obtained by the said dispersion process and said other component contained in the photosensitive coloring composition are mixed, and it is set as a uniform solution. In the manufacturing process of a photosensitive coloring composition, since fine dust is mixed in a liquid in many cases, it is preferable to filter the obtained photosensitive coloring composition with a filter etc.

[Cured material]

The hardened|cured material of this invention is obtained by hardening|curing the photosensitive coloring composition of this invention. The hardened|cured material formed by hardening|curing the photosensitive coloring composition can be used suitably as a coloring spacer.

[Colored spacer]

Next, the colored spacer of this invention comprised from the hardened|cured material of this invention is demonstrated according to the manufacturing method.

(1) support

As a support body for forming a colored spacer, if it has moderate intensity|strength, the material will not be specifically limited. Although a transparent substrate is mainly used, as a material, for example, polyester resins, such as polyethylene terephthalate, polyolefin resins, such as polypropylene and polyethylene, thermoplastics, such as polycarbonate, polymethylmethacrylate, polysulfone, and thermosetting resin sheets such as resin sheets, epoxy resins, unsaturated polyester resins and poly(meth)acrylic resins, and various types of glass. Among these, from a heat resistant viewpoint, glass and heat resistant resin are preferable. Moreover, transparent electrodes, such as ITO and IZO, may be formed into a film on the surface of a board|substrate. It is also possible to form on a TFT array other than a transparent substrate.

The support may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as a silane coupling agent and urethane resin, if necessary, for improvement of surface properties such as adhesion.

The thickness of a transparent substrate is 0.05-10 mm normally, Preferably it becomes the range of 0.1-7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) colored spacer

Although the photosensitive coloring composition of this invention can be used for the use similar to the well-known photosensitive coloring composition for color filters, the formation method is demonstrated about the case where it is used as a coloring spacer below.

Usually, the photosensitive coloring composition is supplied in the form of a film|membrane or a pattern by methods, such as application|coating, on the support body in which a coloring spacer should be formed, and a solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method in which exposure-development is performed. Then, a colored spacer is formed on the support body by performing additional exposure or a thermosetting process as needed.

(3) Formation of colored spacers

[1] How to feed the substrate

The photosensitive coloring composition of this invention is normally melt|dissolved or disperse|distributed to a solvent, and is supplied on a support body. As the supply method, it can implement by a conventionally well-known method, for example, the spinner method, the wire bar method, the flow coat method, the die coat method, the roll coat method, the spray coat method, etc. Moreover, you may supply in the form of a pattern by the inkjet method, the printing method, etc. Especially, according to the die-coating method, the usage-amount of a coating liquid is greatly reduced, and there is no influence of mist etc. adhering when it is spin-coating method, and it is preferable from a general viewpoint, such as the generation|occurrence|production of a foreign material being suppressed.

Although the application amount changes depending on the use, for example, in the case of a colored spacer, as a dry film thickness, it is 0.5 micrometer - 10 micrometers normally, Preferably it is 1 micrometer - 9 micrometers, Especially preferably, it is the range of 1 micrometer - 7 micrometers. am. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire substrate. When the variation is large, defects such as display unevenness may occur in the liquid crystal panel.

However, when forming collectively the colored spacer from which height differs by the photolithographic method using the photosensitive coloring composition of this invention, the height of the finally formed colored spacer differs.

Moreover, as a board|substrate, well-known board|substrates, such as a glass substrate, can be used. In addition, it is preferable that the substrate surface is planar.

[2] Drying method

It is preferable that drying after supplying the photosensitive coloring composition on a board|substrate is based on the drying method using a hotplate, IR oven, and a convection oven. Moreover, you may combine the reduced-pressure drying method which dries in a pressure reduction chamber without raising a temperature.

Drying conditions, such as a drying temperature and drying time, can be suitably selected according to the kind of solvent component, the performance of the dryer to be used, etc. Usually, it is selected from the range of 15 second - 5 minutes at the temperature of 40 degreeC - 130 degreeC, Preferably it is the range of 30 seconds - 3 minutes at the temperature of 50 degreeC - 110 degreeC.

[3] Exposure method

Exposure overlaps a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiates and performs the light source of an ultraviolet-ray or visible light through this mask pattern. When exposing using an exposure mask, the method of making an exposure mask close to the coating film of the photosensitive coloring composition, or arrange|positioning the exposure mask in the position away from the coating film of the photosensitive coloring composition, and exposure through the exposure mask A method of projecting light may also be employed. Moreover, it is also possible by the scanning exposure method by the laser beam which does not use a mask pattern. At this time, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer by oxygen, exposure is carried out in a deoxidized atmosphere or after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer. also be

As a preferred aspect of the present invention, when colored spacers having different heights are simultaneously formed by photolithography, for example, a light-shielding portion (light transmittance 0%) and a plurality of openings, the openings having the highest average light transmittance An exposure mask having (completely transmitting openings) and low average light transmittance openings (intermediately transmitting openings) is used. According to this method, the difference in the remaining film rate is caused by the difference in average light transmittance between the intermediate transmission opening and the fully transmitting opening, ie, the difference in exposure amount.

A method or the like is known in which the intermediate transmission opening is produced by, for example, a matrix-like light-shielding pattern having a microscopic polygonal light-shielding unit. Moreover, as an absorber, the method etc. which control the light transmittance and manufacture with film|membrane of materials, such as a chromium type, a molybdenum type, a tungsten type, a silicon type, are known.

The light source used for said exposure is not specifically limited. Examples of the light source include lamp 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 arcs, fluorescent lamps, argon ion lasers, YAG lasers. and laser light sources such as excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. In the case of irradiating and using light of a specific wavelength, an optical filter may be used.

As the optical filter, for example, a thin film may be of a type capable of controlling the light transmittance at the exposure wavelength, and as the material in that case, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.); MoSi, Si, W, Al, etc. are mentioned.

The exposure dose is usually 1 mJ/cm 2 or more, preferably 5 mJ/cm 2 or more, more preferably 10 mJ/cm 2 or more, usually 300 mJ/cm 2 or less, preferably 200 mJ/cm 2 or less, More preferably, it is 150 mJ/cm<2> or less.

In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 µm or more, preferably 50 µm or more, more preferably 75 µm or more, and usually 500 µm or less, preferably It is 400 micrometers or less, More preferably, it is 300 micrometers or less.

[4] Development method

After performing said exposure, an image pattern can be formed on a board|substrate by image development using the aqueous solution of an alkaline compound, or the organic solvent. The aqueous solution may further contain surfactants, organic solvents, buffers, complexing agents, dyes or pigments.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate. Inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or organic alkaline compounds such as diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. A mixture of 2 or more types may be sufficient as these alkaline compounds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. ; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinates; Amphoteric surfactants, such as alkyl betaines and amino acids, are mentioned.

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

The conditions of the developing treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50°C, particularly 15 to 45°C, particularly preferably 20 to 40°C, and the developing method is an immersion developing method or spray development. It can be based on any method, such as a method, a brush developing method, and an ultrasonic developing method.

[5] Additional exposure and heat curing treatment

The board|substrate after image development may be further exposed by the method similar to said exposure method as needed, and may also be thermosetted. The thermosetting treatment conditions at this time are the temperature in the range of 100 degreeC - 280 degreeC, Preferably it is selected in the range of 150 degreeC - 250 degreeC, and the time is selected in the range of 5 minutes - 60 minutes.

Although the size, shape, etc. of the colored spacer of the present invention are appropriately adjusted according to the specifications of the color filter to which it is applied, the photosensitive coloring composition of the present invention is a colored spacer in which the height of the spacer and the sub-spacer differs by the photolithographic method in particular. In this case, the height of the spacer is usually about 1 to 7 μm, and the sub-spacer has a height lower than that of the spacer by about 0.2 to 1.5 μm.

[Image display device]

The image display apparatus of this invention is equipped with the coloring spacer of this invention.

For example, a color filter having a colored spacer of the present invention described above and a liquid crystal driving-side substrate are bonded together to form a liquid crystal cell, and liquid crystal is injected into the formed liquid crystal cell, thereby providing the colored spacer of the present invention; The image display device of this invention, such as a liquid crystal display device, can be manufactured.

Example

Next, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples without departing from the gist thereof.

The constituent components of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.

<Alkali-soluble resin-I>

It stirred, replacing 145 mass parts of propylene glycol monomethyl ether acetate with nitrogen, and heated up at 120 degreeC. 10 parts by mass of styrene, 85 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.) are added dropwise thereto, and 2,2'-azobis- 8.5 mass parts of 2-methylbutyronitrile was dripped over 3 hours, and also stirring was continued at 90 degreeC for 2 hours. Next, the inside of the reaction vessel was changed to air, and 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were put into 43 parts by mass of acrylic acid, and the reaction was continued at 100°C for 12 hours. Then, 56 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 weight average molecular weight Mw of polystyrene conversion measured by GPC of the alkali-soluble resin-I obtained in this way was 8400, and the acid value was 80 mgKOH/g.

<Alkali-soluble resin-II>

It stirred, replacing 124 mass parts of propylene glycol monomethyl ether acetate with nitrogen, and heated up at 120 degreeC. 4 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, and 4 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are added dropwise thereto, and 2,2'-azobis- 7.2 mass parts of 2-methylbutyronitrile was dripped over 3 hours, and also stirring was continued at 90 degreeC for 2 hours. Next, the inside of the reaction container was changed to air, and 0.6 mass parts of trisdimethylaminomethylphenol and 0.12 mass parts of hydroquinone were thrown into 67 mass parts of acrylic acid, and reaction was continued at 100 degreeC for 12 hours. Then, 15 mass parts of tetrahydrophthalic anhydride (THPA) and 0.6 mass parts of triethylamine were added, and it was made to react at 100 degreeC for 3.5 hours. Thus, the weight average molecular weight Mw of polystyrene conversion measured by GPC of alkali-soluble resin-II obtained in this way was 9000, the acid value was 24 mgKOH/g, and the double bond equivalent was 260 g/mol.

<Dispersant-I>

"BYK-LPN21116" manufactured by Big Chemie (acrylic AB block copolymer comprising an A block having a quaternary ammonium base and a tertiary amino group in the side chain, and a B block having no quaternary ammonium base and tertiary amino group. The amine value is 70 mgKOH/g. Acid value is 1 mgKOH/g or less.)

In the A block of the dispersant-I, the repeating unit of the following formulas (1a) and (2a) is contained, and the repeating unit of the following formula (3a) is contained in the B block. The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of the dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[Formula 50]

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxybutanol

<Photoinitiator-I>

2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2-biimidazole manufactured by Kurogane Chemical Co., Ltd.

<Photoinitiator-II>

Irgacure (registered trademark) 369 manufactured by BASF

<Mercapto compound>

2-mercaptobenzothiazole manufactured by Tokyo Chemical Company

<Photopolymerizable monomer>

Nippon Kayaku Co., Ltd. DPHA (dipentaerythritol hexaacrylate)

<Surfactant>

Megapac F-554 manufactured by DIC

<Additive-I>

Nippon Kayaku Co., Ltd. KAYAMER (registered trademark) PM-21 (Phosphate containing methacryloyl group)

<Additive-II>

Seiko Chemical Co., Ltd. Methylhydroquinone

<Preparation of Pigment Dispersion Liquids 1 to 7>

The pigment, dispersing agent, alkali-soluble resin, and solvent of Table 1 were mixed so that it might become the mass ratio of Table 1, and the liquid mixture was obtained. In addition, the quantity of the solvent derived from a dispersing agent and alkali-soluble resin is also contained in the compounding ratio of the solvent in Table 1.

The dispersion process was performed for this liquid mixture in the range of 25-45 degreeC with a paint shaker for 3 hours. As a bead, a zirconia bead of 0.5 mmφ was used, and 2.5 times the mass of the dispersion was added. After completion of the dispersion, beads and dispersions were separated by a filter to prepare pigment dispersions 1 to 7.

<Preparation of the photosensitive coloring compositions 1-13>

[Examples 1 to 8 and Comparative Examples 1 to 5]

Using the pigment dispersions 1 to 7 prepared above, each component is added so that the ratio of the solid content of each component in the total solid content becomes the blending ratio of Table 2 or Table 3, and further so that the total solid content content is 19 mass% PGMEA was added, stirred and melt|dissolved, and the photosensitive coloring compositions 1-13 were prepared. Using each obtained photosensitive coloring composition, the method mentioned later evaluated.

<Measurement of optical density per unit film thickness (unit OD value)>

The photosensitive coloring composition was apply|coated with the spin coater so that the film thickness after heat-hardening might be set to 1.5 micrometers on a glass substrate, and after drying under reduced pressure for 1 minute, it dried at 90 degreeC for 100 second with a hotplate. The whole surface exposure process was performed to the obtained coating film so that an exposure amount might be set to 60 mJ/cm<2> using the ultraviolet-ray whose intensity|strength in 365 nm is 40 mW/cm<2> without using a mask.

Then, using the developing solution which consists of aqueous solution containing 0.05 mass % of potassium hydroxide and 0.08 mass % of nonionic surfactant ("A-60" manufactured by Kao Corporation), shower development with a water pressure of 0.15 MPa at 25°C After performing for 100 seconds, development was stopped with pure water and washed with water spray. The resist cured film board|substrate was obtained by heat-hardening the said board|substrate at 230 degreeC for 20 minute(s) in oven.

The optical density (OD) of the obtained resist cured film board|substrate was measured with the transmission densitometer 361T (V) by X-Rite, Inc., and the film thickness was measured with Hitachi High-Technologies, Inc. scanning type white interference microscope VS1530. From the optical density (OD) and the film thickness, the optical density per unit film thickness (unit OD value, OD/µm) was calculated and shown in Table 4. In addition, the OD value is a numerical value indicating the light-shielding ability, and the larger the numerical value, the higher the light-shielding property.

<Evaluation of illuminance>

Except having set the exposure amount to 10 mJ/cm<2>, it carried out similarly to the said resist cured film board|substrate, and obtained the board|substrate for illumination intensity evaluation.

The arithmetic mean surface roughness (Sa) of the surface in the range of 10 micrometers x 10 micrometers of the obtained board|substrate was measured with Hitachi High-Technologies company make scanning white interference microscope VS1530, and the following references|standards evaluated roughness. Table 4 shows the measurement results and evaluation results. In addition, the measurement mode was set to focus mode, the magnification of the objective lens was set to 50 times, and the center wavelength of the measurement light was set to 520 nm.

Sa is obtained by dividing the volume of the portion surrounded by the surface-shaped curved surface and the average surface by the measurement area, and the smaller the numerical value, the higher the smoothness.

(evaluation standard of illuminance)

A: 2 nm or less

B: more than 2 nm

<Evaluation of elastic recovery rate>

A glass substrate having an ITO film formed on its surface is used as the substrate, and a mask having a 20 µm opening (a circular opening having a diameter of 20 µm) is used for exposure, and the same as the above-mentioned resist cured film substrate except that the exposure gap is 150 µm. and a colored spacer was obtained.

The elastic recovery rate of the obtained colored spacer was measured in the following procedure. Using a Fischer Scope H-100 (manufactured by Fischer Instruments), using a flat indenter having a measurement temperature of 23°C and a diameter of 50 µm, a load was applied to the colored spacer at a constant speed (5 mN/sec) so that the load was 300 mN The load-displacement curve was obtained by holding for 5 seconds at the time of reaching , and continuously unloading at the same speed. From this load-displacement curve, the maximum displacement H [max] and the final displacement H [Last] (displacement after the load became 0 mN and held for 5 seconds) were measured. Next, the elastic recovery rate was computed by the following formula, and the following reference|standard evaluated. The results are shown in Table 4.

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

(Evaluation criteria for elastic recovery rate)

A: 95% or more

B: less than 95%

<Evaluation of light resistance>

It carried out similarly to the said resist cured film board|substrate, and obtained the board|substrate for light resistance evaluation.

The absorbance in wavelength 450nm of the obtained board|substrate was measured using the Hitachi High-Technologies company make spectrophotometer U-3500.

Next, the said board|substrate was irradiated with the light whose intensity|strength at a wavelength of 450 nm is 19 mW/cm<2> from the film surface side in the environment of 25 degreeC of temperature and 50%RH of relative humidity for 500 hours. The absorbance of the substrate at a wavelength of 450 nm was measured similarly. The change rate of the absorbance at a wavelength of 450 nm was computed by the following formula, it evaluated by the following reference|standard, and the result was shown in Table 5.

Change in absorbance (%) = {(absorbance at 450 nm before irradiation - absorbance at 450 nm after irradiation)/absorbance at 450 nm before irradiation} x 100

(Criteria for evaluation)

A: less than 20%

B: 20% or more

As is clear from Examples 1 to 8 shown in Table 4, the content rate of the colorant is 2 to 20 mass% in the total solid content, including a purple pigment, and the content rate of the purple pigment in the colorant is 50 mass% or more A photosensitive coloring composition It turns out that the colored spacer excellent in surface roughness and mechanical properties can be formed by using.

From the comparison of Example 1 and Comparative Example 1, it turns out that it is excellent in surface roughness by making the content rate of the purple pigment in a coloring agent 50 mass % or more. Since a purple pigment has high dispersibility and is disperse|distributed uniformly in a cured film, it is thought that it is because solubility at the time of image development becomes uniform by containing a lot of purple pigments.

Moreover, from the comparison of Example 1 and Comparative Example 2, it turns out that a mechanical characteristic becomes favorable as the content rate of a coloring agent is 20 mass % or less in the total solid of the photosensitive coloring composition. It is thought that this is because the content rate of alkali-soluble resin and an ethylenically unsaturated compound can be set relatively high by preventing the content rate of a coloring agent from becoming high too much, and the crosslinking density of the colored spacer obtained became high.

In addition, as is clear from the comparison with Comparative Examples 3 and 4, when the content rate of the colorant is less than 2 mass % in the total solid content of the photosensitive coloring composition, the optical density is insufficient, and the content rate of the purple pigment in the colorant is Regardless, the surface roughness is good. Therefore, when the content ratio of the colorant is 2% by mass or more in the total solid content of the photosensitive coloring composition, the optical density becomes good, and it can be seen that the surface roughness may become insufficient depending on the type and ratio of the pigment in the colorant. .

From the comparison of Examples 1 and 5 and Comparative Example 5 shown in Table 5, it turns out that it is excellent in light resistance by making the content rate of the purple pigment in a coloring agent 50 mass % or more. The purple pigment has low absorbance in the vicinity of wavelength 450 nm, and it is considered that it is because it is not easily influenced by the irradiation light of wavelength 450 nm by containing a lot of purple pigments.

Claims (9)

A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photoinitiator, and (d) an ethylenically unsaturated compound,
The content rate of the said (a) coloring agent is 2-20 mass % in the total solid of the photosensitive coloring composition,
(a) the colorant comprises a purple pigment, and
The content rate of the said purple pigment in the said (a) coloring agent is 50 mass % or more, The photosensitive coloring composition characterized by the above-mentioned. The method of claim 1,
The photosensitive coloring composition in which the said purple pigment contains at least 1 sort(s) chosen from the group which consists of CI pigment violet 29 and CI pigment violet 23. 3. The method according to claim 1 or 2,
The photosensitive coloring composition in which the said (a) coloring agent contains an orange pigment further. 4. The method according to any one of claims 1 to 3,
The photosensitive coloring composition whose content rate of the said (b) alkali-soluble resin with respect to 100 mass parts of said (d) ethylenically unsaturated compounds is 150 mass parts or less. 5. The method according to any one of claims 1 to 4,
The photosensitive coloring composition in which said (c) photoinitiator contains the hexaarylbiimidazole compound. 6. The method according to any one of claims 1 to 5,
The photosensitive coloring composition for formation of a colored spacer. Hardened|cured material obtained by hardening|curing the photosensitive coloring composition in any one of Claims 1-6. A colored spacer comprising the cured product according to claim 7. The image display apparatus provided with the colored spacer of Claim 8.