KR102366341B1 - Photosensitive coloring composition, cured product, image display device, and pigment dispersion for image display device - Google Patents

Abstract

(식 (1) 중, Y^- 는 일반식 (2) 로 나타내는 카운터 아니온이다.)Provided is a photosensitive coloring composition that is excellent in electrical reliability after ultraviolet irradiation and has good solvent resistance. The photosensitive coloring composition of this invention contains (a) coloring agent, (b) alkali-soluble resin, (c) photoinitiator, (d) ethylenically unsaturated compound, (e) solvent, and (f) photosensitive coloring containing a dispersing agent As a composition, the optical density per 1 micrometer of film thickness of the cured coating film is 0.5 or more, (f) a dispersing agent is characterized by containing the dispersing agent (f1) which has a repeating unit represented by general formula (1).
[Formula 1]

(In formula (1), Y ^- is a counter anion represented by general formula (2).)

Description

Photosensitive coloring composition, cured product, image display device, and pigment dispersion for image display device

The present invention relates to a photosensitive coloring composition, a cured product, an image display device, and a pigment dispersion for an image display device. Specifically, for example, it relates to a photosensitive coloring composition used for forming a colored spacer in an image display device of a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, and an image display device containing the cured product .

This application claims priority on the basis of Japanese Patent Application No. 2019-162547, filed in Japan on September 6, 2019 and Japanese Patent Application No. 2020-026622, filed on February 19, 2020 in Japan, the content of which invoke it here

A liquid crystal display (LCD) utilizes the property that the arrangement method of liquid crystal molecules is switched by on/off of the voltage with respect to the liquid crystal. On the other hand, each member which comprises the cell of LCD is formed by the method using the photosensitive composition typified by the photolithographic method in many cases. Since this photosensitive composition is easy to form a fine structure and it is easy to process with respect to the board|substrate for large screens, there exists a tendency for the application range to expand further in the future.

However, in the LCD manufactured using the photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electrical properties of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition, thereby causing problems such as display non-uniformity. There are cases. In particular, in a member closer to the liquid crystal layer in a color liquid crystal display, for example, a so-called columnar spacer, a photospacer, etc. used in order to keep the space|interval of 2 board|substrates constant in a liquid crystal panel, etc. The impact is great.

Conventionally, when a spacer having no light-shielding property is used for a TFT-type LCD, the TFT as a switching element may malfunction due to the light passing through the spacer. In order to prevent this, the method of using the spacer (color spacer) which has light-shielding property is examined.

In recent years, with a change in the structure of a panel, a method of collectively forming colored spacers by a photolithography method has been proposed. For example, in patent document 1, the photosensitive coloring composition excellent in reliability which was excellent in light-shielding property and suppressed the elution of the impurity with respect to a solvent by using together several types of organic coloring pigments and a specific photoinitiator is disclosed.

Patent Document 2 discloses a coloring composition excellent in light-shielding properties in a visible region and transmittance in a near-infrared region by using a specific coloring agent together with a dispersing agent having an amino group of a specific structure or the like.

Patent Document 3 discloses that a block copolymer having a specific anion is excellent in heat resistance.

Japanese Patent Laid-Open No. 2016-164623 Japanese Laid-Open Patent Publication No. 2018-169539 International Publication No. 2018/079659

With the change of the recent panel structure, the method of performing ultraviolet irradiation after liquid-crystal cell manufacture for a liquid-crystal orientation improvement has been expanding. When irradiated with ultraviolet rays, a part of the pigment contained in the colored spacer or the like tends to be decomposed to generate impurities, and even in that case, it is required to maintain sufficient electrical reliability.

As a result of this inventor examining about the photosensitive coloring composition containing the dispersing agent described in patent document 1, it was difficult to ensure electrical reliability after ultraviolet irradiation.

The photosensitive coloring composition containing the dispersing agent described in patent document 2 was insufficient in the chemical-resistance (NMP resistance) with respect to the solvent (N-methylpyrrolidone, NMP) at the time of forming an alignment film.

It was difficult for the photosensitive coloring composition containing the dispersing agent described in patent document 3 to ensure electrical reliability before and behind ultraviolet irradiation.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition that is excellent in electrical reliability after ultraviolet irradiation and has good solvent resistance.

As a result of this inventor earnestly examining, by using a specific dispersing agent, it discovered that the said subject was solvable, and came to complete this invention.

That is, the summary of this invention is as follows.

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

An optical density of 0.5 or more per 1 μm of the film thickness of the cured coating film,

The said (f) dispersing agent contains the dispersing agent (f1) which has a repeating unit represented by following General formula (1), The photosensitive coloring composition characterized by the above-mentioned.

[Formula 1]

(in formula (1), R ¹ to R ³ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and two or more of R ¹ to R ³ are bonded to each other to form a cyclic structure may be formed.

R ⁴ is a hydrogen atom or a methyl group.

X is a divalent linking group.

Y ^- is a counter anion represented by the following general formula (2).)

[Formula 2]

(In formula (2), R ⁵ is an alkyl group which may have a substituent.)

[2] The photosensitivity according to [1], wherein the (a) colorant contains at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment. coloring composition.

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

[4] The photosensitive coloring composition according to [3], wherein the black pigment contains an organic black pigment.

[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the content ratio of the (a) coloring agent is 10 mass% or more in total solid content.

[6] The photosensitive coloring composition according to any one of [1] to [5], wherein the amine value of the dispersing agent (f1) is 30 mgKOH/g or more.

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

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

[9] An image display device comprising the cured product according to [8].

[10] A pigment dispersion for an image display device comprising (a) a colorant, (e) a solvent, and (f) a dispersant, comprising:

Said (a) colorant contains a black pigment,

The said (f) dispersing agent contains the dispersing agent (f1) which has a repeating unit represented by following General formula (1), The pigment dispersion liquid for image display apparatuses characterized by the above-mentioned.

[Formula 3]

(in formula (1), R ¹ to R ³ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and two or more of R ¹ to R ³ are bonded to each other to form a cyclic structure may be formed.

R ⁴ is a hydrogen atom or a methyl group.

X is a divalent linking group.

Y ^- is a counter anion represented by the following general formula (2).)

[Formula 4]

(In formula (2), R ⁵ is an alkyl group which may have a substituent.)

[11] The pigment dispersion for an image display device according to [10], wherein the black pigment contains an organic black pigment.

[12] The pigment dispersion for an image display device according to [10] or [11], wherein the amine value of the dispersing agent (f1) is 30 mgKOH/g or more.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the electrical reliability after ultraviolet irradiation, and the photosensitive coloring composition with favorable solvent resistance 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 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 the present invention, "acrylic resin" means a (co)polymer containing (meth)acrylic acid, and a (co)polymer containing (meth)acrylic acid ester having a carboxyl group.

In the present invention, "monomer" is a term relative to a so-called high molecular substance (polymer), and is meant to include dimers, trimers, and oligomers in addition to monomers (monomers) in a narrow sense.

In this invention, "total solid content" means all components other than a solvent contained in the photosensitive coloring composition or a pigment dispersion liquid.

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

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. Unless otherwise specified, an "acid value" represents an acid value in terms of effective solid content, and is calculated by neutralization titration.

Regarding the pigment, "C. I.” means a color index.

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

[Photosensitive Coloring Composition]

The photosensitive coloring composition of the present invention,

(a) colorants

(b) alkali-soluble resin

(c) photoinitiator

(d) ethylenically unsaturated compounds

(e) solvents

(f) dispersants

It contains as an essential component, and, if necessary, further contains other compounding components such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, etc. , Usually, each compounding component is 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 suitable light absorption property, especially a colored spacer, moderate light-shielding property can be acquired.

Moreover, in the photosensitive coloring composition of this invention, the optical density (Hereinafter, it may call "OD per unit film thickness") per 1 micrometer of film thickness of the cured coating film is 0.5 or more. (a) By containing a coloring agent and making OD per unit film thickness more than the said lower limit, the light-shielding property of the hardened|cured material obtained, especially a colored spacer increases.

OD per unit film thickness is computable by measuring the optical density and film thickness of the coating film which hardened the photosensitive coloring composition, and dividing the optical density by the film thickness. Although the manufacturing conditions of a coating film are not specifically limited, For example, the conditions described in the Example mentioned later can be employ|adopted.

In order to make OD per unit film thickness more than the said lower limit, what is necessary is just to adjust appropriately the content rate in the kind of (a) coloring agent, and total solid, for example.

The kind of (a) coloring agent which can be used for the photosensitive coloring composition of this invention is not specifically limited, A pigment may be used and dye may be used. Among these, it is preferable to use a pigment from a durable viewpoint.

(a) Single 1 type may be sufficient as the pigment contained in a coloring agent, and 2 or more types may be sufficient as it. In particular, from a viewpoint of making light shielding uniformly in a visible region and OD per unit film thickness compatible, it is preferable that it is 2 or more types.

(a) Although the kind of pigment which can be used as a coloring agent is not specifically limited, For example, an organic coloring pigment and a black pigment are mentioned. Here, an organic coloring pigment means the organic pigment which shows colors other than black, For example, a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment, and a yellow pigment are mentioned.

It is preferable to use an organic coloring pigment from a viewpoint of suppressing absorption of an ultraviolet-ray among a pigment and making it easy to control the shape and level|step difference of hardened|cured material. Moreover, it is preferable to use a black pigment from a light-shielding viewpoint.

An organic coloring pigment may be used individually by 1 type, but may use 2 or more types together. In particular, from the viewpoint of setting the OD per unit film thickness to 0.5 or more, it is more preferable to use a combination of organic color pigments having different colors, and it is still more preferred to use a combination of organic color pigments exhibiting a color close to black.

Although the chemical structure of these organic coloring pigments is not specifically limited, For example, azo type, phthalocyanine type, quinacridone type, benzimidazolone type, isoindolinone type, dioxazine type, indanthrene type, perylene type are mentioned. there is. Hereinafter, the specific example of the pigment which can be used is shown by a pigment number. “C. I. Pigment Red 2, etc. in "C. I." means a color index.

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, 272 from the point of dispersibility and light-shielding property, and when hardening the photosensitive coloring composition with ultraviolet-ray, it is to use a thing with a low ultraviolet-absorption rate as a red pigment. It is preferable, and it is more preferable to use CI pigment red 254 and 272 from such a viewpoint.

Orange (orange) pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, it is preferable to use CI pigment orange 13, 43, 64, 72 from a viewpoint 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 is used It is preferable to do it, and it is more preferable to use CI pigment orange 64 and 72 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, 60, More preferably, CI Pigment Blue 15: 6 can be 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 rate is used It is preferable to do it, and it is more preferable to use CI Pigment Blue 60 from such a viewpoint.

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 is mentioned.

In addition, from the viewpoint of dispersibility and light-shielding property, it is preferable to use CI Pigment Violet 23, 29, and when curing the photosensitive coloring composition with ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate, , it is more preferable to use CI Pigment Violet 29 from this viewpoint.

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 , 59 can be mentioned. Among these, Preferably, C.I. Pigment Green 7 and 36 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, Preferably, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, More preferably, CI Pigment Yellow 83, 138, 139, 150, 180 is mentioned. there is.

Among these, it is preferable to use at least 1 sort(s) selected from the group which consists of a red pigment, an orange pigment, a blue pigment, and a purple pigment from a viewpoint of the light-shielding property of hardened|cured material, and control of a shape and level|step difference.

Among these, it is preferable to set it as what contains at least 1 type or more of the following pigments from a viewpoint of the light-shielding property of hardened|cured material, and control of a shape and level|step difference.

Red Pigment: C. I. Pigment Red 177, 254, 272

Orange Pigment: C. I. Pigment Orange 43, 64, 72

Blue Pigment: C. I. Pigment Blue 15: 6, 60

Purple Pigment: C. I. Pigment Violet 23, 29

Moreover, in the case of using 2 or more types of organic color pigments together, it is although it does not specifically limit about the combination of an organic color pigment, At least 1 type selected from the group which consists of a red pigment and an orange pigment from a light-shielding viewpoint, and a blue pigment And it is preferable to contain at least 1 sort(s) chosen from the group which consists of a purple pigment.

In addition, the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment and a purple pigment are mentioned. can

As a black pigment, an organic black pigment and an inorganic black pigment are mentioned. Among them, it is preferable to use an organic black pigment from the viewpoint of suppressing the absorption of ultraviolet rays and making it easy to control the shape and level difference of the cured product.

Among organic black pigments, the compound represented by the following general formula (1) (hereinafter, "compound (1) )"), geometric isomers of compound (1), salts of compound (1), and organic black pigments containing at least one selected from the group consisting of salts of geometric isomers of compound (1). (Hereinafter, "the organic black pigment represented by General formula (1)" may be called.) It is preferable to use.

[Formula 5]

In Formula (1), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom, or a chlorine atom;

R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently, a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ^- , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N=CH ₂ , N=CHR ²¹ , N=CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ^— , SO ₂ NH ₂ , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;

At least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be directly may be bonded, or may be bonded to each other via an oxygen atom, a sulfur atom, NH or NR ²¹ bridge;

R ²¹ and R ²² 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. indicates.

Compound (1) and the geometric isomer of compound (1) have the following core structures (provided that the substituents in the structural formula are omitted), and the trans-trans isomer is most likely the most stable.

[Formula 6]

When compound (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, primary ammonium , secondary ammonium, tertiary ammonium, such as trialkylammonium, quaternary ammonium, such as tetraalkylammonium, or a salt compensated with an organometallic complex is preferable. Moreover, when the geometric isomer of compound (1) is anionic, it is preferable that it is the same salt.

In the substituent of general formula (1) and their definition, since there exists a tendency for a shielding rate to become high, the following are preferable. This is because it is considered that the following substituents do not absorb and do not affect the color of the pigment.

R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

R ¹³ and R ¹⁸ 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 ^- , more preferably a hydrogen atom or SO ₃ H; Especially preferably, it is a hydrogen atom.

R ¹¹ and R ¹⁶ 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 ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, more preferably Preferably, R ¹¹ is identical to R ¹⁶ , R ¹² is identical to R ¹⁷ , R ¹³ is identical to R ¹⁸ , R ¹⁴ is identical to R ¹⁹ , and R ¹⁵ is identical to R ²⁰ .

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, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group or 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 silica group, a norbornyl group, and a boryl group. nyl group, norcalyl group, kalyl group, menthyl group, norphinyl group, pinyl group, adamantan-1-yl group, or adamantan-2-yl 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-butene -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) (hereinafter also referred to as “compound (2)”), and a group consisting of a geometric isomer of the compound (2) It is an organic black pigment containing at least 1 sort(s) selected from.

[Formula 7]

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

This organic black pigment is preferably dispersed and used by a dispersing agent, solvent, and method described later. In addition, when the sulfonic acid derivative of compound (1), especially the sulfonic acid derivative of compound (2) is present during dispersion, dispersibility and storage stability may be improved. Therefore, it is preferable that the organic black pigment contains these sulfonic acid derivatives. .

As organic black pigments other than the organic black pigment represented by the said General formula (1), aniline black and perylene black are mentioned, for example.

On the other hand, it is preferable to use an inorganic black pigment from a light-shielding viewpoint. Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black can be preferably used from a viewpoint of light-shielding property and an image characteristic. Examples of carbon black include the following carbon blacks.

Manufactured by Mitsubishi Chemicals: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B

Manufactured by 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, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Manufactured by Cabot Corporation: Monarch (registered trademark, 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, hereinafter the same.) XC72R, ELFTEX (registered trademark)-8

Manufactured by Villa: 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 the carbon black coated with the resin, for example, carbon black described in JP-A-09-71733 can be preferably used. From the viewpoints of volume resistance and dielectric constant, resin-coated carbon black is preferably used.

As carbon black used for the coating process with resin, it is preferable that the total content of Na and Ca is 100 ppm or less. Carbon black is usually Na, Ca, K, Mg, Al, Fe mixed from raw material oil, combustion oil (or gas), reaction stop water, granulated water, and furnace material of a reactor, etc. at the time of manufacture. Ash content, such as the composition, is contained in the order of percent. Among these, although it is common to contain each several hundred ppm or more of Na and Ca, by reducing these, penetration into a transparent electrode (ITO) or another electrode is suppressed, and there exists a tendency for electrical short circuit to be prevented.

As a method of reducing the content of ash containing these Na and Ca, as raw material oil or fuel oil (or gas) and reaction stop water when producing carbon black, carefully selecting those with as little these content as possible and the structure This is possible by minimizing the addition amount of the alkali substance to be adjusted. As another method, a method of removing by dissolving Na or Ca by washing the carbon black produced in the furnace with water, hydrochloric acid, or the like is exemplified.

Specifically, after mixing and dispersing carbon black in water, hydrochloric acid, or hydrogen peroxide solution, when a poorly soluble solvent is added to water, the carbon black migrates to the solvent side, is completely separated from water, and most of the Na present in the carbon black and Ca are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use only the carbon black manufacturing process in which raw materials are carefully selected or the water or acid dissolution method alone. can be 100 ppm or less.

Moreover, it is preferable that resin-coated carbon black is so-called acidic carbon black with a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it becomes possible to coat|cover to a fine unit, and it is preferable. Moreover, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 ml/100 g or less. By setting it as the said range, there exists a tendency for the coating film with favorable light-shielding property to be obtained. The average particle diameter means a number average particle diameter, and it is obtained by particle image analysis in which several fields are taken of pictures taken at tens of thousands of times by electron microscope observation, and about 2000 to 3000 particles of these pictures are measured by an image processing device. Means the equivalent diameter of a circle.

The method for preparing the carbon black coated with the resin is not particularly limited, but for example, after appropriately adjusting the blending amount of the carbon black and the resin, 1. Mix the resin with a solvent such as cyclohexanone, toluene, and xylene and heat it The dissolved resin solution and the suspension in which carbon black and water are mixed are mixed and stirred to separate carbon black and water, water is removed, and the composition obtained by heating and kneading is formed into a sheet, pulverized, and dried. method ; 2. A method of mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and resin, then separating and heating the obtained granular material to remove residual solvent and water; 3. Dissolve carboxylic acid such as maleic acid and fumaric acid in the solvent exemplified above, add carbon black, mix and dry, remove the solvent to obtain carbon black doped with carboxylic acid, and add a resin dry blending by adding ; 4. A reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, and after polymerization and cooling to obtain a reactive group-containing resin from the polymer suspension, carbon black is added thereto and kneaded; a method of reacting black with a reactive group (by grafting carbon black), cooling and pulverizing; etc. can be employed.

The type of resin to be coated is also not particularly limited, but synthetic resins are common, and resins having a benzene ring in their structure are preferable from the viewpoint of dispersibility and dispersion stability because the amphoteric surfactant-like function is stronger.

Specific synthetic resins include thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glyphtal resins, epoxy resins, and alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, and polybutylene terephthalate. Thermoplastics such as phthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, polyetheretherketone, etc. A resin may be used. As for the coating amount of resin with respect to carbon black, 1-30 mass % is preferable with respect to the total amount of carbon black and resin, and there exists a tendency for coating|covering to be sufficient by making it more than the said lower limit. On the other hand, by using below the said upper limit, adhesion of resin is prevented, and there exists a tendency for dispersibility to be good.

The carbon black formed by coating with resin in this way can be used as a light-shielding material for a colored spacer according to a conventional method, and a color filter having this colored spacer as a component can be manufactured by a conventional method. When such carbon black is used, there is a tendency that a colored spacer having a high light-shielding rate and a low surface reflectance can be achieved at low cost. Moreover, it is estimated that there also exists a function which encloses Ca and Na in carbon black by coat|covering the carbon black surface with resin.

It is preferable to use these pigments disperse|distributed 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 of this invention 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 on a sufficiently diluted photosensitive coloring composition (usually diluted and prepared with a pigment concentration of about 0.005 to 0.2 mass%. However, if there is a concentration recommended by the measuring instrument, it follows the concentration.) 25 Measure at °C.

Moreover, the photosensitive coloring composition of this invention WHEREIN: Coloring agents, such as an organic coloring pigment and a black pigment, may be used individually by 1 type, and may use 2 or more types together. Among these, it is preferable to use together an organic black pigment and an organic coloring pigment from a viewpoint of making it easy to control a shape and a level|step difference, On the other hand, it is preferable to use carbon black and an organic coloring pigment together from a viewpoint of light-shielding property.

Moreover, you may use dye other than the organic coloring pigment and black pigment mentioned above. Examples of the dye usable as a color material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. there is.

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, and CI Mordant Black 7 are mentioned.

Examples of the anthraquinone dye include CI Pad 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 is mentioned.

In addition, as a phthalocyanine type dye, for example, CI pad blue 5, as a quinoneimine type dye, for example, CI basic blue 3, CI basic blue 9, as a quinoline type dye, for example, CI solvent yellow 33, Examples of CI acid yellow 3 and CI disperse yellow 64 as nitro dyes include CI acid yellow 1, CI acid orange 3, and CI disperse yellow 42.

<(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 carboxy 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 resin A urethane resin, a novolak-type resin, and a polyvinyl phenol-type resin are mentioned. inter alia,

(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) Epoxy (meth) acrylate-based resin is a reaction between an epoxy compound (epoxy resin) and α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety It is a resin obtained by making the hydroxyl group produced|generated by react with the compound which further has two or more substituents which can react with hydroxyl groups, such as a polybasic acid and/or its anhydride.

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

Moreover, the resin obtained by making the carboxy group of the 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 in terms of 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.

As the (b1) epoxy (meth) acrylate-based resin used in the present invention, in particular the following epoxy (meth) acrylate-based resin (b1-1) and/or epoxy (meth) acrylate-based resin (b1-2) (Hereinafter, it may be called "carboxy-group-containing epoxy (meth)acrylate-type resin.") is preferably used from a viewpoint of developability and reliability.

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

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

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

Alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid 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 .

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 be used. 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 divalence or more than bivalence phenolic hydroxyl group is preferable, and a monomer may be sufficient as it or a polymer may be sufficient as it.

As a kind of epoxy resin used as a raw material, for example, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, biphenyl no Volac-type epoxy resin, naphthalene novolak-type epoxy resin, polyaddition product of dicyclopentadiene and phenol or cresol, epoxy resin that is a reaction product of epihalohydrin, adamantyl group-containing epoxy resin, fluorene-type epoxy resin It can be used preferably, and among these, what has an aromatic ring in a principal chain can be used more preferably.

Moreover, as an epoxy resin, For example, a bisphenol A epoxy resin (For example, Mitsubishi Chemical Corporation "jER (trademark, the same.) 828", "jER1001", "jER1002", "jER1004" etc.), an epoxy resin obtained by reaction of an alcoholic hydroxyl group of a bisphenol A epoxy resin with epichlorhydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76° C.)), bisphenol F-type resin (for example, "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), the alcoholic hydroxyl group and epichlorhydrin of a bisphenol F-type epoxy resin an epoxy resin obtained by the reaction of (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S-type epoxy resin, biphenyl glycidyl ether (e.g., "YX-4000" manufactured by Mitsubishi Chemical Co., Ltd.), phenol novolac-type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation) , "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolak type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same.)-102S" manufactured by Nippon Kayaku Co., Ltd.) , "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), trisphenol methane type epoxy resin (for example, “EPPN (registered trademark, hereinafter the same.)-501”, “EPPN-502”, “EPPN-503” manufactured by Nippon Kayaku Co., Ltd., alicyclic epoxy resin (“Celoxide (registered trademark, hereinafter the same)” manufactured by Daicel Co., Ltd.) .) 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, manufactured by Nippon Kayaku Co., Ltd.) of 「NC-7300」), the following general formula (B1 ) to (B4) epoxy resins can be preferably used. Specifically, for example, "XD-1000" by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1), and "NC-3000" manufactured by Nippon Kayaku Corporation as an epoxy resin represented by the following general formula (B2) ', "E-201" manufactured by Osaka Organic Chemical Industries, Ltd. as an epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Shin-Nittetsu Sumikin Chemicals as an epoxy resin represented by the following general formula (B4) can

[Formula 8]

In the general formula (B1), a is an average value and represents a number from 0 to 10, and R ¹¹¹ is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 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 9]

In the general formula (B2), b1 and b2 each independently represent an average value and represent a number of 0 to 10, R ¹²¹ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 to 10 carbon atoms. of a cycloalkyl group, 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 as or different from each other.

[Formula 10]

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 11]

In the above general 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 even if it has a substituent An alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent is represented, and * represents a bond.

[Formula 12]

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

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

As α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy 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)acryloyloxypropylsuccinic acid, 2 -(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmalee Acid, 2-(meth)acryloyloxybutyl succinic 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 A monomer obtained by adding an acid (anhydride) such as (anhydride) succinic acid, (anhydride) phthalic acid, (anhydride) maleic acid, or the like to a hydroxyalkyl (meth) acrylate or pentaerythritol tri (meth) acrylate; (meth)acrylic acid dimer etc. are mentioned.

Among these, (meth)acrylic acid is especially preferable from a point of a sensitivity.

As a method of adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group to the epoxy resin, a known method can be used. For example, in the presence of an esterification catalyst, at a temperature of 50 to 150° C., an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin. . 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, each component of the epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may be used by selecting each component one by one, 2 You may use more than a species together.

The amount of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 with respect to 1 equivalent of the epoxy groups of the epoxy resin. -1.1 equivalents. By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to be greater than or equal to the above lower limit, insufficient introduction of unsaturated groups can be suppressed, and continued polybasic acid and/or anhydride thereof It also tends to be easy to make a reaction with a sufficient thing as well. On the other hand, by setting it to below the upper limit, it is possible to suppress the residual of the unreacted product of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group, and it tends to make the curing properties good. It is observed.

Polybasic acids and/or anhydrides thereof include, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid , endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

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.

The addition reaction of the polybasic acid and/or its anhydride can be carried out using a known method, and an α,β-unsaturated monocarboxylic acid with an epoxy resin or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. The target product can be obtained by continuing the reaction under the same conditions as in the addition 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 further, 20 to 140 mgKOH It is preferable to be in the range of /g. The alkali developability tends to become favorable by setting it as more than the said lower limit, and there exists a tendency for hardening performance to become favorable by setting it as below the said upper limit.

During the addition reaction of a polybasic acid and/or anhydride thereof, polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane and 1,2,3-propanetriol (polyhydric alcohol) may be added to introduce a multi-branched structure. In this case, there is no restriction|limiting in particular in the mixing order of a polybasic acid and/or its anhydride, and a polyfunctional alcohol. By heating, a polybasic acid and/or its The anhydride undergoes an addition reaction.

By using a polyhydric alcohol, (b1) the molecular weight of the epoxy (meth)acrylate resin can be increased, branching can be introduced into the molecule, and there is a tendency that the molecular weight and the viscosity can be balanced. Moreover, the introduction rate of an acidic radical into a molecule|numerator can be increased, and there exists a tendency for a balance, such as a sensitivity and adhesiveness, to be easy to achieve.

Examples of the carboxyl group-containing epoxy (meth)acrylate-based resins other than those described above include those described in Korean Patent Application Laid-Open No. 10-2013-0022955 A.

The weight average molecular weight (Mw) of the carboxyl group-containing 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 3000 or more, More preferably, it is 4000 or more, Especially preferably, it is 5000 or more, Usually, it is 10000 or less, Preferably it is 8000 or less, More preferably, it is 7000 or less. For example, 1000-10000 are preferable, 1500-10000 are more preferable, 1500-8000 are still more preferable, 2000-8000 are still more preferable, 2000-7000 are especially preferable. There exists a tendency which can suppress that the solubility with respect to a developing solution becomes high too much by setting it as more than the said lower limit. It exists in the tendency for solubility with respect to a developing solution to be easy to make favorable by carrying out below the said upper limit.

Although the acid value of the carboxyl group-containing epoxy (meth)acrylate-based resin is not particularly limited, 10 mgKOH/g or more is preferable, 20 mgKOH/g or more is more preferable, and 40 mgKOH/g or more is still more preferable, 50 mgKOH/g or more is still more preferable, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 120 mgKOH/g or less is still more preferable, 100 mgKOH/g or less g or less is particularly preferred. For example, 10 mgKOH/g - 200 mgKOH/g are preferable, 20 mgKOH/g - 150 mgKOH/g are more preferable, 40 mgKOH/g - 120 mgKOH/g are still more preferable , more preferably 50 mgKOH/g to 100 mgKOH/g. By setting it as more than the said lower limit, there exists a tendency for moderate image development solubility to be acquired. It exists in the tendency which can suppress that image development advances too much and film melt|dissolution by setting it as below the said upper limit.

The chemical structure of the epoxy (meth) acrylate-based resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-I) (hereinafter, It may be abbreviated as "(b1-I) epoxy (meth) acrylate resin") and/or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b1-II) (hereinafter referred to as "(b1-I) epoxy (meth) acrylate resin"). , "(b1-II) epoxy (meth)acrylate resin" may be abbreviated.)

[Formula 13]

In formula (b1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (b1-I) may be further substituted by arbitrary substituents.

[Formula 14]

In formula (b1-II), R ¹³ each independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R ¹⁵ and R ¹⁶ are each independently; The divalent aliphatic group which may have a substituent is represented, m and n each independently represent the integer of 0-2, * represents a bond.

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

First, an epoxy (meth)acrylate-based resin having a partial structure represented by the general formula (b1-I) will be described in detail.

[Formula 15]

In formula (b1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (b1-I) may be further substituted by arbitrary substituents.

(R ¹² )

In the formula (b1-I), R ¹² represents a divalent hydrocarbon group which may have a substituent.

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

Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among these, a linear thing is preferable from a viewpoint of image development solubility. On the other hand, a ring-shaped thing is preferable from a viewpoint of the penetration reduction of the developing solution with respect to an exposed part. The carbon number is normally 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, 1-15 are more preferable, and 1-10 are still more preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the divalent linear aliphatic group include a methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. Among these, a methylene group is preferable from a viewpoint of the rigidity of frame|skeleton.

As a divalent branched aliphatic group, as a side chain to the above-mentioned divalent linear aliphatic group, for example, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group A structure having a group, a sec-butyl group, and a tert-butyl group is exemplified.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Usually, it is 1 or more, 2 or more are preferable, Moreover, it is 12 or less normally, and 10 or less are preferable. For example, 1-12 are preferable, 1-10 are more preferable, and 2-10 are still more preferable. By using more than the said lower limit, it becomes a strong film|membrane and there exists a tendency for board|substrate adhesiveness to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and groups in which two hydrogen atoms have been removed from rings, such as dicyclopentadiene and dicyclopentane. Among these, groups in which two hydrogen atoms have been removed from the dicyclopentadiene ring, the dicyclopentane ring and the adamantane ring are preferable from the viewpoint of rigidity of the skeleton.

As a substituent which the divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; and a carboxyl group. Among these, the unsubstituted thing is preferable from a viewpoint of synthetic|combination easiness.

Moreover, as a divalent aromatic cyclic group, a divalent aromatic hydrocarbon cyclic group and a divalent aromatic heterocyclic group are mentioned. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Aromatic hydrocarbon ring groups include, for example, 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 tri A phenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned.

Moreover, as an aromatic heterocyclic ring in an aromatic heterocyclic group, a monocyclic ring may be sufficient as it and a condensed ring may be sufficient as it. Aromatic heterocyclic groups include, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole, having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, and a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring and an azulene ring.

Among these, from the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

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

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

Although the number of divalent aliphatic groups is not specifically limited, Usually, 1 or more, 2 or more are preferable, Usually 10 or less, 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, 2-3 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Although the number of divalent aromatic ring groups is not specifically limited, Usually, 1 or more, 2 or more are preferable, Usually 10 or less, 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, 2-3 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the group linking one or more divalent aliphatic groups to one or more divalent aromatic ring groups include groups represented by the following formulas (b1-I-A) to (b1-I-F). Among these, the group represented by the following formula (b1-I-A) is preferable from the viewpoints of rigidity of the skeleton and hydrophobization of the film.

[Formula 16]

k represents 1 or 2. 1 is preferable from a viewpoint of adhesiveness and patterning property, and, as for k, 2 is preferable from a viewpoint of NMP tolerance. Moreover, in the (b1-I) epoxy (meth)acrylate, both the partial structure in which k is 1 and the partial structure in which k is 2 may contain.

As described above, the benzene ring in the formula (b1-I) may be further substituted with any substituent. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is also not specifically limited, One may be sufficient as it, and two or more may be sufficient as it.

Among these, it is preferable that it is unsubstituted from a viewpoint of a patterning characteristic.

Further, the partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1) from the viewpoint of synthesis simplicity.

[Formula 17]

In the formula (b1-I-1), R ¹¹ , R ¹² and k have the same meanings as in the formula (b1-I), R ^X represents a hydrogen atom or a polybasic acid residue, and * represents a bond. The benzene ring in formula (b1-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 the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydro Phthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid are mentioned.

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

As described above, the benzene ring in the formula (b1-I-1) may be further substituted with an optional substituent. As the substituent, those exemplified for the benzene ring in formula (b1-I) can be preferably employed.

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

Further, the number of partial structures represented by the above formula (b1-I) contained in one molecule of (b1-I) epoxy (meth)acrylate-based resin is not particularly limited, but 1 or more is preferable, and 3 or more is more It is preferable, and 20 or less are preferable, and 15 or less are still more preferable. 1-20 are preferable, 1-15 are more preferable, 3-15 are still more preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

(b1-I) The weight average molecular weight (Mw) of the epoxy (meth)acrylate-based resin in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited, but preferably 1000 or more, and 1500 or more More preferably, 2000 or more are more preferable, 3000 or more are still more preferable, 4000 or more are particularly preferable, 5000 or more are most preferable, and 30000 or less are preferable, 20000 or less are more preferable, 10000 or less is more preferable, and 8000 or less is particularly preferable. For example, 1000-30000 are preferable, 1500-20000 are more preferable, 1500-10000 are still more preferable, 1500-8000 are still more preferable, 2000-8000 are especially preferable, 2000-7000 are especially preferable. Do. There exists a tendency for the residual-film rate of the photosensitive coloring composition to become favorable by using more than the said lower limit. There exists a tendency for resolution to become favorable by using below the said upper limit.

(b1-I) 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, 40 mgKOH/g or more More preferably, 50 mgKOH/g or more is more preferable, 80 mgKOH/g or more is particularly preferable, and 200 mgKOH/g or less is preferable, and 150 mgKOH/g or less is more preferable, 130 mgKOH/g or less is still more preferable, and 100 mgKOH/g or less is particularly preferable. For example, 10 mgKOH/g - 200 mgKOH/g are preferable, 20 mgKOH/g - 200 mgKOH/g are more preferable, 40 mgKOH/g - 150 mgKOH/g are still more preferable , more preferably 50 mgKOH/g to 130 mgKOH/g, and particularly preferably 80 mgKOH/g to 100 mgKOH/g or less. By using more than the said lower limit, image development solubility improves and there exists a tendency for resolution to become favorable. There exists a tendency for the residual-film rate of the photosensitive coloring composition to become favorable by using below the said upper limit.

Specific examples of (b1-I) epoxy (meth)acrylate-based resins are given below. In addition, * in an example represents a bond.

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

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

Next, the epoxy (meth)acrylate-type resin which has a partial structure represented by the said general formula (b1-II) is demonstrated in detail.

[Formula 22]

In formula (b1-II), R ¹³ each independently represents a hydrogen atom or a methyl group, R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R ¹⁵ and R ¹⁶ are each independently; The divalent aliphatic group which may have a substituent is represented, m and n each independently represent the integer of 0-2, * represents a bond.

(R ¹⁴ )

In the general formula (b1-II), R ¹⁴ 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, 2 or more are preferable, Moreover, it is 10 or less normally, 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, 2-3 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Moreover, carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 30 or less are more preferable, 20 or less are still more preferable, 15 or less is 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 setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

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, an adamantane ring, a cyclododecane ring. can be heard Among these, an adamantane ring is preferable from a viewpoint of the residual-film rate of a photosensitive coloring composition, and a resolution.

On the other hand, the number of rings which an aromatic cyclic group has is although it does not specifically limit, Usually, 1 or more, 2 or more are preferable, 3 or more are more preferable, And usually 10 or less, 5 or less are preferable, and 4 or less are more desirable. 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 setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

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, Moreover, 40 or less are preferable, 30 or more are preferable. The following is more preferable, 20 or less are still more preferable, and 15 or less are especially preferable. For example, 4-40 are preferable, 6-40 are more preferable, 8-30 are still more preferable, 10-20 are still more preferable, 12-15 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. There exists a tendency for a patterning characteristic to become favorable by setting it as below the said upper limit.

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, and a fluorene ring. 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 bivalent aliphatic group, a divalent aromatic ring group, 1 or more divalent aliphatic groups, and 1 or more 2 The group which connected the valent aromatic ring group is mentioned.

Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among these, a linear thing is preferable from a viewpoint of developing solubility, on the other hand, a cyclic thing is preferable from a viewpoint of the permeation reduction of the developing solution with respect to an exposed part. The carbon number is normally 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 setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the divalent linear aliphatic group include a methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. Among these, a methylene group is preferable from a viewpoint of the rigidity of frame|skeleton.

As a divalent branched aliphatic group, for example, a methyl group, an ethyl group, n-propyl group, an iso-propyl group, n-butyl group, iso-butyl group as a side chain to the above-mentioned divalent linear aliphatic group. A structure having a group, a sec-butyl group, and a tert-butyl group is exemplified.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Usually, 1 or more, 2 or more are preferable, Moreover, it is 10 or less normally, 5 or less are preferable, and 3 or less are still more preferable. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By using more than the said lower limit, it becomes a strong film|membrane and there exists a tendency for board|substrate adhesiveness to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. and groups in which two hydrogen atoms have been removed from the ring. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

As a substituent which the divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; and a carboxyl group. Among these, the unsubstituted thing is preferable from a viewpoint of synthetic|combination easiness.

Moreover, as a divalent aromatic cyclic group, a divalent aromatic hydrocarbon cyclic group and a divalent aromatic heterocyclic group are mentioned. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Aromatic hydrocarbon ring groups include, for example, 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 tri A phenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned.

Moreover, as an aromatic heterocyclic ring in an aromatic heterocyclic group, a monocyclic ring may be sufficient as it and a condensed ring may be sufficient as it. Aromatic heterocyclic groups include, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole, having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, and a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring and an azulene ring. Among these, a benzene ring or a naphthalene ring which has two free valences is preferable from a viewpoint of a patterning characteristic, and the benzene ring which has two free valences is more preferable.

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

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

Although the number of divalent aliphatic groups is not specifically limited, Usually, 1 or more, 2 or more are preferable, Usually 10 or less, 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, 2-3 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Although the number of divalent aromatic ring groups is not specifically limited, Usually, 1 or more, 2 or more are preferable, Usually 10 or less, 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, 2-3 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the group linking one or more divalent aliphatic groups to one or more divalent aromatic ring groups include groups represented by the above formulas (b1-I-A) to (b1-I-F). Among these, the group represented by the said formula (b1-I-C) from a viewpoint of the rigidity of a frame|skeleton and the hydrophobization of a film|membrane is preferable.

With respect to these divalent hydrocarbon groups, the bonding mode of the cyclic hydrocarbon group as 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 a cyclic hydrocarbon group as a side chain, The aspect which comprised the cyclic hydrocarbon group which is a side chain including one carbon atom of an aliphatic group is mentioned.

(R ¹⁵ , R ¹⁶ )

In the general formula (b1-II), R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent.

Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among these, a linear thing is preferable from a viewpoint of developing solubility, on the other hand, a cyclic thing is preferable from a viewpoint of the permeation reduction of the developing solution with respect to an exposed part. The carbon number is normally 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 setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, surface roughening does not generate|occur|produce easily, and there exists a tendency for adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the divalent linear aliphatic group include a methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. Among these, a methylene group is preferable from a viewpoint of the rigidity of frame|skeleton.

As a divalent branched aliphatic group, as a side chain to the above-mentioned divalent linear aliphatic group, for example, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group A structure having a group, a sec-butyl group, and a tert-butyl group is exemplified.

Although the number of rings which a bivalent cyclic aliphatic group has is not specifically limited, Usually, it is 1 or more, 2 or more are preferable, Moreover, it is 12 or less normally, and 10 or less are preferable. For example, 1-12 are preferable and 2-10 are more preferable. By using more than the said lower limit, it becomes a strong film|membrane and there exists a tendency for board|substrate adhesiveness to become favorable. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

Examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and groups in which two hydrogen atoms have been removed from the dicyclopentadiene ring. Among these, groups obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring are preferable from the viewpoint of rigidity of the skeleton.

As a substituent which the divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; and a carboxyl group. Among these, the unsubstituted thing is preferable from a viewpoint of synthetic|combination easiness.

(m, n)

In the said general formula (b1-II), m and n each independently represent the integer of 0-2. By setting it as more than the said lower limit, patterning titration becomes favorable and there exists a tendency for surface roughening to become hard to generate|occur|produce, and there exists a tendency for developability to become favorable by setting it as below the said upper limit. From a viewpoint of developability, it is preferable that m and n are 0. On the other hand, it is preferable that m and n are 1 or more from a viewpoint of patterning titration and surface roughness.

Moreover, it is preferable that the partial structure represented by the said general formula (b1-II) is a partial structure represented by the following general formula (b1-II-1) from a viewpoint of adhesiveness to a board|substrate.

[Formula 23]

In the formula (b1-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meaning as in the formula (b1-II), and R ^α is an optionally substituted monovalent cyclic hydrocarbon group. , p represents an integer greater than or equal to 1, and * represents a bond. The benzene ring in formula (b1-II-1) may be further substituted by arbitrary substituents.

(R ^α )

In the general formula (b1-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, 2 or more are preferable, Moreover, it is 6 or less normally, 4 or less are preferable, and 3 or less are more preferable. For example, 1-6 are preferable, 1-4 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. There exists a tendency for a patterning characteristic to become favorable by setting it as below the said upper limit.

Moreover, carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 30 or less are more preferable, 20 or less are still more preferable, 15 or less is particularly preferred. 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, 8-15 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. There exists a tendency for a patterning characteristic to become favorable by setting it as below the said upper limit.

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, an adamantane ring, a cyclododecane ring. can be heard Among these, an adamantane ring is preferable from a viewpoint of a strong film|membrane characteristic.

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, it is 10 or less normally, and 5 or less are preferable. For example, 1-10 are preferable, 1-5 are more preferable, 2-5 are still more preferable, and 3-5 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. There exists a tendency for a patterning characteristic to become favorable by setting it as 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 setting it more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce, Moreover, there exists a tendency for patterning characteristic to become favorable by setting it as below the said upper limit.

As an aromatic ring in an aromatic ring group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring are mentioned. Among these, a fluorene ring is preferable from a viewpoint of developing solubility.

Examples of the substituent that the cyclic hydrocarbon group may have include 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. A C1-C5 alkyl group, such as a push group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; and a carboxyl group. Among these, from a viewpoint of synthetic|combination easiness, unsubstitution is preferable.

Although p 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. There exists a tendency for a film hardening degree and a residual film rate to become favorable by using more than the said lower limit. There exists a tendency for developability to become favorable by setting it as below the said upper limit.

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

As described above, the benzene ring in the formula (b1-II-1) may be further substituted with any substituent. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is also not specifically limited, One may be sufficient as it, and two or more may be sufficient as it.

Among these, it is preferable that it is unsubstituted from a viewpoint of a patterning characteristic.

Specific examples of the partial structure represented by the above formula (b1-II-1) are given below.

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

Further, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-2) from the viewpoints of rigidity of the skeleton and membrane hydrophobicity.

[Formula 29]

In the formula (b1-II-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meaning as in the formula (b1-II), and R ^β is an optionally substituted divalent cyclic hydrocarbon group. and * represents a bond. The benzene ring in formula (b1-II-2) may be further substituted by arbitrary substituents.

(R ^β )

In the formula (b1-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, 2 or more are preferable, Moreover, it is 10 or less normally, and 5 or less are preferable. For example, 1-10 are preferable and 2-5 are more preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

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. There exists a tendency for film|membrane roughness at the time of image development to be suppressed by setting it as more than the said lower limit. By setting it below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease at the time of image development, and there exists a tendency for resolution to improve.

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, an adamantane ring, a cyclododecane ring. can be heard Among these, an adamantane ring is preferable from a viewpoint of film|membrane reduction at the time of image development, and a resolution.

On the other hand, although the number of rings which an aromatic cyclic group has is although it does not specifically limit, Usually, it is 1 or more, 2 or more are preferable, 3 or more are more preferable, Moreover, it is 10 or less normally, and 5 or less are preferable. For example, 1-10 are preferable, 1-5 are more preferable, 2-5 are still more preferable, and 3-5 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it as below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease, and there exists a tendency for resolution to improve.

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, 40 or less are preferable, 30 or less are more preferable, 20 or less is more preferable, and 15 or less is particularly preferable. For example, 4-40 are preferable, 6-30 are more preferable, 8-20 are still more preferable, 10-15 are especially preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it as below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease, and there exists a tendency for resolution to improve.

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 developable viewpoint.

Examples of the substituent that the cyclic hydrocarbon group may have include 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. A C1-C5 alkyl group, such as a push group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; and a carboxyl group. Among these, from a viewpoint of synthetic|combination simplicity, unsubstitution is preferable.

Among these, from the viewpoint of suppression of film reduction and resolution, it is preferable that R ^β is a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.

On the other hand, from the viewpoint of patterning characteristics, it is preferable that R ^β is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

As described above, the benzene ring in the formula (b1-II-2) may be further substituted with any substituent. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is also not specifically limited, One may be sufficient as it, and two or more may be sufficient as it.

Moreover, the benzene ring of 2 may be connected via a substituent. As a substituent in this case, divalent groups, such as -O-, -S-, -NH-, and -CH ₂ -, are mentioned.

Among these, it is preferable that it is unsubstituted from a viewpoint of a patterning characteristic. Moreover, it is preferable that it is a methyl group substitution from a viewpoint of making film|membrane reduction|decrease etc. less likely to generate|occur|produce.

Specific examples of the partial structure represented by the formula (b1-II-2) are given below. In addition, * in an example represents a bond.

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

It is preferable that the partial structure represented by the said Formula (b1-II) is a partial structure represented by a following formula (b1-II-3) from a viewpoint of a coating-film residual-film rate and a patterning characteristic.

[Formula 34]

In the formula (b1-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in the formula (b1-II), and R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid. Further, another OH group is removed and may be shared with R ^Z in another molecule represented by the formula (b1-II-3), that is, a plurality of formulas (b1-II-) through R ^Z 3) may be connected.

Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydro Phthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, and biphenyl tetracarboxylic acid are mentioned.

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

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

Moreover, although the number of the partial structures represented by the said Formula (b1-II) contained in 1 molecule of (b1-II) epoxy (meth)acrylate-type resin is not specifically limited, 1 or more is preferable, 3 or more are more It is preferable, and 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, and 3-10 are still more preferable. By setting it as more than the said lower limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to become hard to generate|occur|produce. By setting it as below the said upper limit, it is easy to suppress deterioration of a sensitivity and film|membrane decrease, and there exists a tendency for resolution to improve.

(b1-II) The weight average molecular weight (Mw) of the epoxy (meth)acrylate-based resin in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited, but preferably 1000 or more, and 2000 or more More preferably, 20000 or less are more preferable, 10000 or less are still more preferable, 7000 or less are still more preferable, and 5000 or less are especially preferable. For example, 1000-30000 are preferable, 1000-20000 are more preferable, 1000-10000 are still more preferable, 2000-7000 are still more preferable, 2000-5000 are especially preferable. There exists a tendency for a patterning characteristic to become favorable by setting it as more than the said lower limit. By setting it as below the said upper limit, a strong film|membrane is easy to be obtained, and there exists a tendency for surface roughening to not generate|occur|produce easily.

(b1-II) 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, 40 mgKOH/g or more is further Preferably, 60 mgKOH/g or more is more preferable, 80 mgKOH/g or more is particularly preferable, 100 mgKOH/g or more is most preferable, and 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, and 120 gKOH/g or less is still more preferable. For example, 10 mgKOH/g - 200 mgKOH/g are preferable, 20 mgKOH/g - 200 mgKOH/g are more preferable, 40 mgKOH/g - 150 mgKOH/g are still more preferable , more preferably 60 mgKOH/g to 150 mgKOH/g, particularly preferably 80 mgKOH/g to 120 gKOH/g, particularly preferably 100 mgKOH/g to 120 gKOH/g. There exists a tendency for a strong film|membrane to become easy to be obtained by setting it as more than the said lower limit. By carrying out below the said upper limit, image development solubility improves and there exists a tendency for resolution to become favorable.

Carboxylic group containing epoxy (meth)acrylate-type resin may be used individually by 1 type, and may mix and use 2 or more types of resin.

Moreover, you may use, replacing a part of the above-mentioned carboxy group containing epoxy (meth)acrylate-type resin with other binder resin. That is, you may use together carboxyl group containing epoxy (meth)acrylate-type resin and other binder resin. In this case, it is preferable that the ratio of the carboxyl group-containing epoxy (meth)acrylate-type resin in (b) alkali-soluble resin shall be 50 mass % or more, It is more preferable to set it as 60 mass % or more, 70 It is more preferable to set it as mass % or more, and it is especially preferable to set it as 80 mass % or more, and it is 100 mass % or less normally.

Moreover, as (b) alkali-soluble resin, it is preferable to use (b2) acrylic copolymer resin from a compatibility viewpoint with a pigment, a dispersing agent, etc., and what was described in Unexamined-Japanese-Patent No. 2014-137466 can be used preferably.

As the acrylic copolymer resin, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylenically unsaturated monomers (hereinafter “unsaturated monomer”) (b2-2)").

As an unsaturated monomer (b2-1), For example, unsaturated monocarboxylic acids, such as (meth)acrylic acid, a crotonic acid, (alpha)- chloracrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; Mono[(meth)acryloyloxyalkyl] of polyhydric carboxylic acid more than divalent, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] ester; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

These unsaturated monomers (b2-1) can be used individually or in mixture of 2 or more types.

Moreover, as an unsaturated monomer (b2-2), For example, N-substituted maleimides, such as N-phenyl maleimide and N-cyclohexyl maleimide;

aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene;

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

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane vinyl ethers such as;

and macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

These unsaturated monomers (b2-2) can be used individually or in mixture of 2 or more types.

In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. % am. By copolymerizing an unsaturated monomer (b2-1) in such a range, there exists a tendency for the photosensitive coloring composition excellent in alkali developability and storage stability to be obtained.

As a copolymer of an unsaturated monomer (b2-1) and an unsaturated monomer (b2-2), Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. Hei10, for example. -31308, Japanese Unexamined Patent Publication No. Hei 10-300922, Japanese Unexamined Patent Publication No. Hei 11-174224, Japanese Unexamined Patent Publication No. Hei 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japanese Unexamined Patent Publication No. 2004-101728 copolymers disclosed in the preceding paragraph.

Although the copolymer of an unsaturated monomer (b2-1) and an unsaturated monomer (b2-2) can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680. The structure, Mw, and Mw/Mn can also be controlled by the method disclosed by the call, International Publication No. 2007/029871.

In addition, you may use resin of International Publication No. 2016/194619 and International Publication No. 2017/154439.

<(c) Photoinitiator>

(c) The photoinitiator 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; The hexaarylbiimidazole derivatives described in Unexamined-Japanese-Patent No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in Japanese Patent Application Laid-Open No. 10-39503; α-aminoalkylphenone derivatives; The oxime ester type compound described in Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2006-36750, etc. is mentioned.

Examples of the metallocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluoro). Phenyl-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoro Phenyl-1-yl), dicyclopentadienyl titanium di (2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di (2,4-difluorophenyl-1-yl) , di(methylcyclopentadienyl)titaniumbis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl)titaniumbis(2,6-difluoro phenyl-1-yl) and dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyrro-1-yl)-phenyl-1-yl].

Examples of the hexaarylbiimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5- Bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4, 5-diphenylimidazole dimer and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer are mentioned.

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 and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaph). tyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 -ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

As α-aminoalkylphenone derivatives, for example, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4- Dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal) Cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone are mentioned.

As a photoinitiator, an oxime ester type compound is especially effective from the point of a sensitivity and plate-making property, For example, when using the alkali-soluble resin containing a phenolic hydroxyl group, the oxime ester type which is excellent in such a sensitivity especially. Compounds are useful. Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, it is highly sensitive to a small amount, and is stable against thermal reaction, and is stable to a small amount. It is possible to obtain a highly sensitive photosensitive coloring composition.

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, usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably less than 10. For example, a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group are mentioned as a specific example of an alkyl group.

Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy 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 is 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, it is preferable that it is 5 or more. Moreover, from a developable viewpoint, it is preferable that it is 30 or less, It is more preferable that it is 20 or less, It is more preferable that it is 12 or less.

Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group, and among these, a phenyl group or a naphthyl group is preferable from the viewpoint of developability, and a phenyl group is more preferable.

Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy 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, these The linked group is preferable, and the linked alkoxy group is more preferable.

Among these, from the viewpoint of developability, R ^21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having a linked alkoxy group as a substituent.

Moreover, as R ^21b , an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted diphenyl sulfide group are mentioned. Among these, the carbazolyl group which may be substituted from a viewpoint of a sensitivity is preferable. From a viewpoint of electrical reliability, the diphenyl sulfide group which may be substituted is preferable.

In addition, the carbon number of the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility and sensitivity to a solvent, usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, More preferably, it is 10 or less, More preferably, it is 5 or less. For example, an acetyl group, a propanoyl group, and a butanoyl group are mentioned as an alkanoyl group.

Examples of the substituent which the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group, and from the viewpoint of easiness of synthesis, it is preferably unsubstituted.

Moreover, although carbon number of the aryl group in R ^22a is not specifically limited, From a viewpoint of solubility to a solvent and a sensitivity, it is 7 or more normally, Preferably it is 8 or more, Moreover, it is normally 20 or less, Preferably 15 or less, More preferably, it is 10 or less. A benzoyl group and a naphthoyl group are mentioned as an aryl group.

Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group, and from the viewpoint of easiness of synthesis, it is preferable that the substituent 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.

The initiator described in Unexamined-Japanese-Patent No. 2016-133574 is also used preferably from the point which contamination of the liquid-crystal layer by a colorant 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, For example, 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. Hei 5, for example. Heterocyclic coumarin pigment described in -289335, 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. 3-239703 and Japanese Unexamined Patent Publication No. 5-289335, Japanese Unexamined Patent Publication No. 6-19240 Pyromethene dye described in Japanese Patent Application Laid-Open No. 47-2528, Japanese Unexamined Patent Publication 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 which has 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 is mentioned.

Among these sensitizing dyes, an amino group-containing sensitizing dye is preferable, and the compound which has an amino group and a phenyl group in the same molecule|numerator is more preferable. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3 Benzophenone-type compounds, such as '- 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 are preferable, and 4,4'-dialkylaminobenzophenone is particularly desirable.

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

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

<(d) ethylenically unsaturated compound>

The photosensitive coloring composition of this invention contains (d) 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. Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkylester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and monoester of polyhydric or monohydric alcohol are mentioned. .

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 or less. and more preferably 7 or less. For example, 2-8 pieces are preferable, 2-7 pieces are more preferable, 4-7 pieces are still more preferable, and 5-7 pieces are especially preferable. There exists a tendency to become high sensitivity by setting it as more than the said lower limit. There exists a tendency for the solubility with respect to a solvent to improve by using 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; Ester obtained by esterification of polyhydric hydroxy compounds, such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound, and unsaturated carboxylic acid and polybasic carboxylic acid is mentioned.

As ester of an aliphatic polyhydroxy compound and unsaturated carboxylic acid, For example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylolethane triacrylate, pentaerythritol di Aliphatic polyhydroxys such as acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Acrylic acid esters of compounds, methacrylic acid esters replacing these acrylates with methacrylate, itaconic acid esters replacing itaconate, crotonic acid esters replacing cronate, and maleic acid ester replacing maleate. there is.

As ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, for example Acrylic acid ester and methacrylic acid ester of aromatic polyhydroxy compounds, such as these are mentioned.

The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but for example, 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, as the polyfunctional ethylenic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth)acrylic acid ester are reacted with a urethane obtained (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, are useful.

Urethane (meth) acrylates, 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 Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (made by Nippon Synthetic Chemical Industry Co., Ltd.) is mentioned.

Among these, it is preferable to use (meth)acrylic-acid alkylester as (d) ethylenically unsaturated compound from a sclerosis|hardenable viewpoint, 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 contains the (e) solvent. (e) By including a solvent, (a) a coloring agent can be disperse|distributed or dissolved in a solvent, and application|coating becomes easy.

The photosensitive coloring composition of this invention is normally (a) coloring agent, (b) alkali-soluble resin, (c) photoinitiator, (d) ethylenically unsaturated compound, (f) dispersing agent, and other used as needed. Various materials are used in the state melt|dissolved or disperse|distributed to a solvent. Among the solvents, an organic solvent is preferable from the viewpoint of dispersibility and applicability.

It is preferable to select a thing with a boiling point of 100-300 degreeC from a viewpoint of applicability|paintability among organic solvents, and it is more preferable that it is 120-280 degreeC. 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.

Examples of the organic solvent include 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 monoethyl ether, and propylene glycol monoethyl ether. -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 Glycol monoalkyl ethers such as , dipropylene glycol monomethyl ether, 3-methoxybutanol, 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 isobutylate, 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-methoxy propyl propionate, 3- chain or cyclic esters such as butyl methoxypropionate 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; can be heard

Commercially available organic solvents include, for example, Mineral Spirit, Barsol #2, Afco #18 Solvent, Afco Thinner, Socal Solvent No.1 and No.2, Solvesso #150, Shell TS28 Solvent, Carbitol , ethyl carbitol, butyl carbitol, methyl cellosolve (“Cellosolve” is a registered trademark.

The same hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all trade names) can be used.

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, it is preferable to select a thing with a boiling point of 100-200 degreeC, and it is more preferable that it is 120-170 degreeC.

Among the organic solvents, the glycol alkyl ether acetates are preferable from the viewpoint of good balance of coating properties and surface tension, and relatively high solubility of the constituent components in the composition.

Moreover, although glycol alkyl ether acetate 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 preferable from the viewpoint of solubility of the constituents in the composition. In addition, glycol monoalkyl ethers have high polarity, and when the amount added is too large, pigments tend to agglomerate, and storage stability such as increased viscosity of the photosensitive coloring composition obtained thereafter tends to decrease. Therefore, glycol monoalkyl ethers in a solvent 5 mass % - 30 mass % are preferable, and, as for the ratio of liquid, 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 material defect due to precipitation and solidification of the colorant at the tip of the slit nozzle. From the viewpoint of such a high effect, among the various solvents mentioned above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable.

When using a high boiling point solvent together, 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 preferred. By setting it to more than the above lower limit, for example, there is a tendency that it can be suppressed that a color material is precipitated and solidified at the tip of the slit nozzle and causes a foreign matter defect, and by setting it below the above upper limit, the drying temperature of the composition is suppressed from slowing down, There exists a tendency which can suppress problems, such as the tact defect of a reduced pressure drying process, and the pin mark of a prebaking.

Moreover, 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 them. In this case, it does not matter even if it does not contain separately the high boiling point solvent of 150 degreeC or more boiling point.

As preferred high boiling point solvents, among the various solvents described above, for example, 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, and triacetin are mentioned.

<(f) dispersant>

The photosensitive coloring composition of this invention contains (f) a dispersing agent. (f) By containing a dispersing agent, (a) a coloring agent can be disperse|distributed stably.

The (f) dispersing agent in the photosensitive coloring composition of this invention contains the dispersing agent (f1) (Hereinafter, it may call a "dispersing agent (f1)") which has a repeating unit represented by the following general formula (1).) .

[Formula 36]

(in formula (1), R ¹ to R ³ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and two or more of R ¹ to R ³ are bonded to each other to form a cyclic structure may be formed.

R ⁴ is a hydrogen atom or a methyl group.

X is a divalent linking group.

Y ^- is a counter anion represented by the following general formula (2).)

[Formula 37]

(In formula (2), R ⁵ is an alkyl group which may have a substituent.)

The dispersing agent (f1) is a dispersing agent having an ammonium group and a counter anion of an alkylsulfonic acid ion. The alkylsulfonic acid ion is an ester-derived anion and is stably bonded to an ammonium group. Therefore, even when immersed in an amine solvent such as N-methylpyrrolidone (NMP), the dispersant is not easily liberated from the colorant and is stable, and the dispersant is adsorbed to the surface of the colorant and the covered state is maintained, and a part of the colorant It is estimated that there is little eluting as an impurity.

On the other hand, since the counter anion of the general formula (2) is stably bound to an ammonium group as a sulfonate ion derived from an ester, even when an excess dispersant not adsorbed to the pigment remains in the cured product, it is a liquid crystal as a sulfonate ion. Since it is not easily liberated in the middle, it is thought that voltage retention becomes hard to become low by not affecting the orientation of a liquid crystal easily. In particular, it is not easily released even after UV irradiation, and it is estimated that the voltage retention does not become low.

(R ¹ to R ³ )

In said Formula ( ¹ ), R1 ^- R3 is each independently the alkyl group which may have a substituent, or the aryl group which may have a substituent.

Examples of the alkyl group for R ¹ to R ³ include a linear, branched, or cyclic alkyl group, and from the viewpoint of voltage retention after UV irradiation and NMP resistance, linear is preferable.

Although carbon number of an alkyl group is not specifically limited, 10 or less are preferable, 6 or less are more preferable, 2 or less are still more preferable, and it is 1 or more normally. By setting it below the said upper limit, there exists a tendency for the stability with time of a dispersion liquid to improve.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and from the viewpoint of stability over time of the dispersion, a methyl group or an ethyl group is preferable, and a methyl group is more preferable. .

As a substituent which the alkyl group may have, Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Aralkyl groups, such as a benzyl group and a phenethyl group; Aryl groups, such as a phenyl group and a naphthyl group, etc. are mentioned, From a dispersibility viewpoint, it is preferable that it is unsubstituted.

Examples of the aryl group for R ¹ to R ³ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.

Although carbon number of an aryl group is not specifically limited, 24 or less are preferable, 18 or less are more preferable, 12 or less are still more preferable, Usually, it is 6 or more. There exists a tendency for dispersibility to improve by using below the said upper limit.

As an aryl group, a phenyl group, a naphthyl group, and anthracenyl group are mentioned, for example, From a dispersibility viewpoint, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

As a substituent which the aryl group may have, For example, alkyl groups, such as a methyl group and an ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Aralkyl groups, such as a benzyl group and a phenethyl group, are mentioned, From a dispersibility viewpoint, it is preferable that it is unsubstituted.

In the formula (1), two or more of R ¹ to R ³ may be bonded to each other to form a cyclic structure, and as the cyclic structure, for example, a nitrogen-containing 5 to 7 membered ring and a heterocyclic monocyclic ring or a condensed ring formed by condensing two thereof. It is preferable that it does not have aromaticity, and, as for a nitrogen-containing heterocyclic ring, a saturated ring is more preferable. Specifically, the following are mentioned.

[Formula 38]

(In the formula, R is any of R ¹ to R ³ . In addition, these cyclic structures may further have a substituent. * represents a bond.)

Among these, from the viewpoint of voltage retention after ultraviolet irradiation and NMP resistance, R ¹ to R ³ are each independently preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, a methyl group or an ethyl group It is more preferable, and it is especially preferable that it is a methyl group.

(X)

In the formula (1), X is a divalent linking group.

Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ⁶ - group, a -COOR ⁷ - group (provided that R ⁶ and R ⁷ ) is a single bond, a C1-C10 alkylene group, or a C2-C10 ether group (alkyloxyalkyl group) is mentioned each independently, From a dispersibility viewpoint, ^-COOR7- group is preferable. Among R ⁷ , from the viewpoint of temporal stability of the dispersion, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is still more preferable.

(Y ^- )

In the formula (1), Y ⁻ is a counter anion represented by the following general formula (2).

[Formula 39]

(In formula (2), R ⁵ is an alkyl group which may have a substituent.)

(R ⁵ )

Examples of the alkyl group for R ⁵ include linear, branched, or cyclic alkyl groups, and from the viewpoint of voltage retention after UV irradiation, linear is preferable.

Although carbon number of an alkyl group is not specifically limited, 6 or less are preferable, 4 or less are more preferable, 2 or less are still more preferable, and it is 1 or more normally. There exists a tendency for the voltage retention after ultraviolet irradiation to become high by setting it as below the said upper limit. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and from the viewpoint of voltage retention after UV irradiation, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

As a substituent which the alkyl group may have, For example, Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom, are mentioned, From a viewpoint of the voltage retention after ultraviolet irradiation, it is preferable that it is unsubstituted.

Among these, from a viewpoint of voltage retention after ultraviolet irradiation, it is preferable that R< ⁵ > is an unsubstituted alkyl group, It is more preferable that it is a methyl group or an ethyl group, It is still more preferable that it is a methyl group.

Although the dispersing agent (f1) has a repeating unit represented by the said General formula (1), it may also have another repeating unit.

It is preferable that the dispersing agent (f1) has a repeating unit represented by the following general formula (3) from a viewpoint of the voltage retention before and after ultraviolet irradiation.

[Formula 40]

(In formula (3), R ⁸ and R ⁹ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent. R ⁸ and R ⁹ may combine with each other to form a cyclic structure .

R ¹⁰ is a hydrogen atom or a methyl group.

Z is a divalent linking group.)

In said Formula (3), R<^8> and R<^9> are each independently the alkyl group which may have a substituent, or the aryl group which may have a substituent. As the alkyl group which may have a substituent, and the aryl group which may have a substituent, what was illustrated as ^{R1 -} R3 in said Formula (1) can be employ|adopted preferably.

In the formula (3), R ⁸ and R ⁹ may be bonded to each other to form a cyclic structure. Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensing two of them. It is preferable that it does not have aromaticity, and, as for a nitrogen-containing heterocyclic ring, a saturated ring is more preferable. Specifically, the following are mentioned.

[Formula 41]

(These cyclic structures may further have a substituent. * represents a bond.)

In the formula (3), Z is a divalent linking group. As a divalent coupling group, what was illustrated as X in said Formula (1) is employable preferably.

Moreover, it is preferable that a dispersing agent (f1) has a repeating unit represented by the following general formula (4) from a viewpoint of improving the compatibility with respect to a solvent and alkali-soluble resin, and improving dispersion stability.

[Formula 42]

(In formula (4), R ¹¹ is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

R ¹² is a hydrogen atom or a methyl group.)

(R ¹¹ )

Examples of the alkyl group for R ¹¹ include a linear, branched, or cyclic alkyl group, and from the viewpoint of compatibility with a solvent or alkali-soluble resin, a linear one is preferable, and It is preferable that it is a branched chain type from a viewpoint of affinity for.

Although carbon number of an alkyl group is not specifically limited, Usually, 1 or more, 2 or more are preferable, 4 or more are more preferable, 10 or less are preferable, 8 or less are more preferable, 6 or less are still more preferable. There exists a tendency for affinity to a pigment to be improved by setting it as more than the said lower limit. By using below the said upper limit, there exists a tendency for compatibility with respect to a solvent or alkali-soluble resin to improve and to improve dispersibility.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an ethylhexyl group. From the viewpoint of compatibility with a solvent or alkali-soluble resin, A methyl group and an ethyl group are preferable, and a methyl group is more preferable.

As a substituent which the alkyl group may have, For example, Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Aryl groups, such as a phenyl group and a naphthyl group, are mentioned, From a viewpoint of compatibility with respect to a solvent and alkali-soluble resin, it is preferable that it is unsubstituted, and it is preferable that it is a viewpoint of affinity with respect to a pigment.

Examples of the aryl group for R ¹¹ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.

Although carbon number of an aryl group is not specifically limited, Usually, 6 or more, and 16 or less are preferable, 12 or less are more preferable, and 10 or less are still more preferable. There exists a tendency for affinity with respect to a pigment to be improved by using below the said upper limit. As an aryl group, a phenyl group, a naphthyl group, and anthracenyl group are mentioned, for example, From a dispersibility viewpoint, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

As a substituent which the aryl group may have, For example, alkyl groups, such as a methyl group and an ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Aryl groups, such as a phenyl group and a naphthyl group; Aralkyl groups, such as a benzyl group and a phenethyl group, are mentioned, From a dispersibility viewpoint, it is preferable that it is unsubstituted.

Among these, from the viewpoint of compatibility with a solvent or alkali-soluble resin, R ¹¹ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, still more preferably a methyl group, a butyl group, or an ethylhexyl group. .

Moreover, it is preferable that a dispersing agent (f1) has a repeating unit represented by the following general formula (5) from a compatible viewpoint with respect to a solvent and alkali-soluble resin.

[Formula 43]

(In formula (5), R ¹³ is a methylene group, an ethylene group, or a propylene group.

R ¹⁴ is a methyl group, an ethyl group, or a propyl group.

R ¹⁵ is a hydrogen atom or a methyl group.

n is an integer from 1 to 20.)

Although R ¹³ is a methylene group, an ethylene group, or a propylene group, an ethylene group is preferable from a compatible viewpoint with respect to a solvent and alkali-soluble resin.

Although R ¹⁴ is a methyl group, an ethyl group, or a propyl group, a methyl group or an ethyl group is preferable from a compatible viewpoint with respect to a solvent or alkali-soluble resin, and an ethyl group is more preferable.

Although n is an integer of 1-20, 1 or more is preferable, 2 or more are more preferable, 10 or less are preferable and 5 or less are more preferable. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable.

There exists a tendency for the compatibility with respect to a solvent or alkali-soluble resin to improve by setting it as more than the said lower limit. There exists a tendency for the affinity to a pigment to increase and to improve dispersibility by setting it as below the said upper limit.

Although the content rate of the repeating unit represented by the said General formula (1) in the dispersing agent (f1) (Hereinafter, it may call "repeating unit (1)") is not specifically limited, 2 mol% in all repeating units More preferably, 5 mol% or more is more preferable, 7 mol% or more is still more preferable, 10 mol% or more is still more preferable, 12 mol% or more is particularly preferable, and 50 mol% or less is preferable. and 40 mol% or less is more preferable, 30 mol% or less is still more preferable, 20 mol% or less is still more preferable, and 15 mol% or less is especially preferable. For example, 2 mol% to 50 mol% are preferable, 5 mol% to 40 mol% are more preferable, 7 mol% to 30 mol% are still more preferable, and 7 mol% to 20 mol% are still more preferable. and 7 mol% to 15 mol% are particularly preferable. By setting it as more than the said lower limit, there exists a tendency for the stability with time of a dispersion liquid to become favorable, and by setting it as below the said upper limit, there exists a tendency for dispersibility to become favorable.

When the dispersing agent (f1) contains the repeating unit represented by the general formula (3) (hereinafter, sometimes referred to as "repeating unit (3)"), the content ratio is not particularly limited, but all repeating units 5 mol% or more is preferable, 10 mol% or more is more preferable, 12 mol% or more is still more preferable, 15 mol% or more is especially preferable, and 50 mol% or less is preferable, and 40 mol% or less is preferable. is more preferable, 30 mol% or less is still more preferable, and 20 mol% or less is particularly preferable. For example, 5 mol% to 50 mol% are preferable, 10 mol% to 40 mol% are more preferable, 12 mol% to 30 mol% are still more preferable, and 15 mol% to 20 mol% are particularly preferable. . There exists a tendency for dispersibility to become favorable by setting it as more than the said lower limit. By setting it as below the said upper limit, there exists a tendency for the stability with time of a dispersion liquid to become favorable.

When the dispersant (f1) contains the repeating unit (3), the content ratio of the repeating unit (1) to the total of the repeating unit (1) and the repeating unit (3) is usually 5 mol% or more, and 10 mol% More preferably, 20 mol% or more is more preferable, 25 mol% or more is still more preferable, 30 mol% or more is particularly preferable, and usually 100 mol% or less, 80 mol% or less is preferable, and 60 mol% or less is preferable. mol% or less is more preferable, 50 mol% or less is still more preferable, and 40 mol% or less is especially preferable. For example, 5 mol% to 100 mol% are preferable, 10 mol% to 80 mol% are more preferable, 20 mol% to 60 mol% are still more preferable, and 25 mol% to 50 mol% are still more preferable. and 30 mol% to 40 mol% are particularly preferable. There exists a tendency for the voltage retention after ultraviolet irradiation and NMP tolerance to become favorable by setting it as more than the said lower limit. By setting it as below the said upper limit, there exists a tendency for the stability with time of a dispersion liquid to become favorable.

When the dispersing agent (f1) contains the repeating unit represented by the general formula (4) (hereinafter, sometimes referred to as "repeating unit (4)"), the content ratio is not particularly limited, but in all repeating units 20 mol% or more is preferable, 30 mol% or more is more preferable, 40 mol% or more is still more preferable, 50 mol% or more is still more preferable, 60 mol% or more is especially preferable, and 90 mol% or more or less is preferable, 80 mol% or less is more preferable, 70 mol% or less is still more preferable, and 65 mol% or less is especially preferable. For example, 20 mol% - 90 mol% are preferable, 30 mol% - 90 mol% are more preferable, 40 mol% - 80 mol% are still more preferable, 50 mol% - 80 mol% are still more preferable and 60 mol% to 80 mol% are particularly preferable. There exists a tendency for affinity to a pigment to be improved by setting it as more than the said lower limit. There exists a tendency to improve the compatibility with respect to a solvent or alkali-soluble resin by using below the said upper limit.

When the dispersing agent (f1) contains the repeating unit represented by the general formula (5) (hereinafter, sometimes referred to as “repeating unit (5)”), the content ratio is not particularly limited, but in all repeating units 1 mol% or more is preferable, 2 mol% or more is more preferable, 3 mol% or more is still more preferable, 30 mol% or less is preferable, 20 mol% or less is more preferable, 15 mol% or less is It is still more preferable, 10 mol% or less is still more preferable, and 5 mol% or less is especially preferable. For example, 1 mol% to 30 mol% are preferable, 1 mol% to 20 mol% are more preferable, 2 mol% to 15 mol% are still more preferable, and 2 mol% to 10 mol% are still more preferable. and 3 mol% to 5 mol% are particularly preferable. By setting it as more than the said lower limit, there exists a tendency for compatibility with respect to a solvent and alkali-soluble resin to be improved. There exists a tendency for affinity with respect to a pigment to be improved by using below the said upper limit.

When the dispersing agent (f1) has the repeating unit (1) and the repeating unit (3), from the viewpoint of dispersibility, a B block having the repeating unit (1) and the repeating unit (3), the repeating unit (1) and the repeating unit It is preferable that it is a block copolymer which has an A block which does not have (3). The block copolymer is preferably an A-B block copolymer or an A-B-A block copolymer.

In the B block, the repeating unit (1) and the repeating unit (3) may be contained in either random copolymerization or block copolymerization mode. Further, the repeating unit (1) and the repeating unit (3) may be contained in each of two or more types in the B block, and in that case, each repeating unit is contained in the B block in either random copolymerization or block copolymerization mode. it may be

When the dispersing agent (f1) has the repeating unit (4) or the repeating unit (5), they may be contained in the A block, or may be contained in any aspect of random copolymerization or block copolymerization. In addition, the repeating unit (4) and the repeating unit (5) may be contained in each of two or more types in the A block, and in that case, each repeating unit is contained in the A block in either random copolymerization or block copolymerization mode. it may be

Repeating units other than repeating units (4) and (5) may be contained in the A 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 N-methacryloylmorpholine.

Although the amine titer of a dispersing agent (f1) is not specifically limited, 20 mgKOH/g or more is preferable, 30 mgKOH/g or more is more preferable, 40 mgKOH/g or more is still more preferable, 45 mgKOH/g or more This is particularly preferable, and 150 mgKOH/g or less is preferable, 100 mgKOH/g or less is more preferable, 80 mgKOH/g or less is still more preferable, and 60 mgKOH/g or less is particularly preferable. For example, 20 mgKOH/g - 150 mgKOH/g are preferable, 30 mgKOH/g - 100 mgKOH/g are more preferable, 40 mgKOH/g - 80 mgKOH/g are still more preferable , 45 mgKOH/g to 60 mgKOH/g are particularly preferred. There exists a tendency for dispersibility to become favorable by setting it as more than the said lower limit. By setting it below the said upper limit, there exists a tendency for the stability with time of a dispersion liquid to improve. The amine titer is expressed by the amount of the base per 1 g of the solid content of the dispersing agent (f1) and the mass of the equivalent KOH.

Although the acid value of a dispersing agent (f1) is not specifically limited, From a dispersibility viewpoint, 10 mgKOH/g or less is preferable, 5 mgKOH/g or less is more preferable, 1 mgKOH/g is still more preferable, 0 mg KOH/g is particularly preferred.

Although the weight average molecular weight of a dispersing agent (f1) is not specifically limited, 3000 or more are preferable, 5000 or more are more preferable, 7000 or more are still more preferable, 100000 or less are preferable, 50000 or less are more preferable, 10000 or more are preferable. The following are more preferable. For example, 3000-100000 are preferable, 5000-50000 are more preferable, 7000-10000 are still more preferable. There exists a tendency for dispersibility to improve by setting it as more than the said lower limit. By setting it below the said upper limit, there exists a tendency for the stability with time of a dispersion liquid to improve.

In addition, in the dispersing agent of the present invention, due to the presence of the counter anion Y ⁻ , the weight average molecular weight cannot be sufficiently measured. In that case, the theoretical molecular weight calculated from the weight average molecular weight value before adding Y ⁻ there are cases where it is used.

Although the theoretical molecular weight of a dispersing agent (f1) is not specifically limited, 3000 or more are preferable, 5000 or more are more preferable, 7000 or more are still more preferable, 100000 or less are preferable, 50000 or less are more preferable, 10000 or less is more preferable. For example, 3000-100000 are preferable, 5000-50000 are more preferable, 7000-10000 are still more preferable. There exists a tendency for dispersibility to improve by setting it as more than the said lower limit. By setting it below the said upper limit, there exists a tendency for the stability with time of a dispersion liquid to improve.

The manufacturing method of a dispersing agent (f1) is not specifically limited, A well-known method is employable. For example, it can manufacture by making the compound represented by the following general formula (2') react with respect to the precursor of the dispersing agent (f1) containing a repeating unit (3).

[Formula 44]

(In formula (2'), R ⁵ has the same meaning as in the formula (2). R ⁵⁰ has the same meaning as any of R ¹ to R ³ in the formula (1).)

(f) dispersing agent in the photosensitive coloring composition of this invention may contain dispersing agents other than a dispersing agent (f1) (Hereinafter, it may call "another dispersing agent.").

As another dispersing agent, from the viewpoint of dispersion stability, for example, as a functional group, a carboxy group; or a base thereof; a primary, secondary or tertiary amino group; quaternary ammonium base; A dispersant having a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is preferable. Among them, a basic functional group, for example, a primary, secondary, or tertiary amino group; quaternary ammonium base; A dispersing agent having a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is more preferable.

Moreover, when dispersing a pigment, a polymer dispersing agent is preferable from a viewpoint of being able to disperse|distribute with a small amount of a dispersing agent.

In addition, 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 and a diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

As such a polymer dispersing agent, for example, as a trade name, EFKA (trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Bikchemi), Disparon (registered trademark, manufactured by Kusumoto Chemicals). , SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical), and Azisper (registered trademark, manufactured by Ajinomoto, Ltd.).

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).

1 type may be used for another dispersing agent, and may use 2 or more types together.

<Other compounding components of the photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, in addition to the components described above, additives such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds and polymerization inhibitors can be appropriately blended. .

(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 and a phosphoric acid group containing compound are preferable.

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

Examples of the silane coupling agent include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclo). Epoxysilanes such as hexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, 3-ureido Isocyanate silanes, such as ureidosilanes, such as propyl triethoxysilane, and 3-isocyanate propyl triethoxysilane, are mentioned. Epoxysilane-type silane coupling agents are especially preferable.

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 45]

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

These phosphoric acid group containing compounds may be used individually by 1 type, and may use 2 or more types together.

(2) surfactant

The photosensitive coloring composition of this invention may 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 or silicone-based surfactant is effective in terms of applicability.

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

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.

As the pigment derivative, for example, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perylene Non-type, diketopyrrolopyrrole type, and dioxazine type|system|group derivatives are mentioned, Among them, a phthalocyanine type and a quinophthalone type are preferable.

As a substituent of the pigment derivative, for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group, etc. are added directly to the pigment skeleton or an alkyl group, an aryl group , those bonded through a heterocyclic group or the like are mentioned, and a sulfonic acid group is preferable. Moreover, two or more of these substituents may be substituted by one pigment frame|skeleton.

Examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. there is. 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 exposing, for example, when crosslinking agents, such as a melamine compound, exist. Among photo-acid generators, the solubility with respect to the solvent with respect to a solvent, especially the solubility with respect to the solvent used for the photosensitive coloring composition, the large thing is preferable. For example, diphenyliodonium, ditolyliodonium, phenyl(p-anisyl)iodonium, bis(m-nitrophenyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p- diaryliodonium such as chlorophenyl)iodonium, bis(n-dodecyl)iodonium, p-isobutylphenyl(p-tolyl)iodonium, and p-isopropylphenyl(p-tolyl)iodonium; Chloride, bromide, or borofluoride salt, hexafluorophosphate salt, hexafluoro arsenate salt, aromatic sulfonate salt of triarylsulfonium, such as triphenylsulfonium, tetrakis (pentafluorophenyl) borate salt; sulfonium organoboron complexes such as diphenylphenacylsulfonium(n-butyl)triphenylborate; and triazine compounds such as 2-methyl-4,6-bistrichloromethyltriazine and 2-(4-methoxyphenyl)-4,6-bistrichloromethyltriazine.

(5) crosslinking agent

A crosslinking agent can be further added to the photosensitive coloring composition of this invention, For example, a melamine or a guanamine type compound can be used. As these crosslinking agents, the melamine or guanamine type compound represented by following General formula (6) is mentioned, for example.

[Formula 46]

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 , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each 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 aryl group having 6 to 12 carbon atoms is typically a phenyl group, 1-naphthyl group or 2-naphthyl group, and these phenyl groups or naphthyl groups may be substituted with a substituent such as an alkyl group, an alkoxy group, or a halogen atom. Carbon number of an alkyl group and an alkoxy group is 1-6, respectively. As the alkyl group represented by R ⁶⁸ , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

To the melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1), for example, hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine.

[Formula 47]

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

In the guanamine-based compound corresponding to the general formula (6), that is, the compound in which R ⁶¹ in the general formula (6) is aryl, for example, tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxy methylbenzoguanamine, tetraethoxymethylbenzoguanamine.

A crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. For example, 2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxy Methyl) perhydro-1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethyleneurea or its dimethyl ether, 3,5-bis( and hydroxymethyl)perhydro-1,3,5-oxadiazin-4-one (common name dimethyloluron) or its dimethyl ether, tetramethylolglyoxaldiurein, or its tetramethylether. .

These crosslinking agents may be used individually by 1 type, and may use 2 or more types together. 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, a mercapto compound can also be added for the improvement of the adhesiveness with respect to a board|substrate.

Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, and 1,4-dimethylmercaptobenzene. , Butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristio Glycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis (3-mercaptobutylate), butanediol bis (3-mer) captobutylate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropanetris(3-mercaptobutylate), pentaerythritol tetrakis(3-mercaptobutylate), pentaeryth Ritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutylate), butanediol bis (3-mercaptoisobutylate), trimethylolpropane tris (3-mercaptoisobutylate) rate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione having a heterocyclic ring A mercapto compound and an aliphatic polyfunctional mercapto compound are mentioned. These can use various things individually by 1 type or in mixture of 2 or more types.

(7) polymerization inhibitor

You may make the photosensitive coloring composition of this invention contain a polymerization inhibitor from a viewpoint of shape control of hardened|cured material. Since it inhibits radical polymerization of a coating film lower layer by containing a polymerization inhibitor, it is thought that a taper angle (angle which the support body in hardened|cured material end surface and hardened|cured material make) can be controlled.

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 can be used individually by 1 type or in mixture of 2 or more types.

(b) When manufacturing alkali-soluble resin, a polymerization inhibitor may be contained in resin, and you may use it as a polymerization inhibitor of this invention, In resin other than a polymerization inhibitor, the same or different polymerization inhibitor. You may add at the time of photosensitive coloring composition manufacture.

When the photosensitive coloring composition contains a polymerization inhibitor, the content rate is although it does not specifically limit, Usually 0.0005 mass % or more in the total solid of the photosensitive coloring composition, Preferably it is 0.001 mass % or more, More preferably, 0.01 mass % or more. and usually 0.3 mass% or less, preferably 0.2 mass% or less, and more preferably 0.1 mass% or less. For example, 0.0005 mass % - 0.3 mass % are preferable, 0.001 mass % - 0.2 mass % are more preferable, 0.01 mass % - 0.1 mass % are still more preferable. There exists a tendency for the shape of hardened|cured material to be controllable by using more than the said lower limit. It exists in the tendency which required sensitivity can be maintained by using below the said upper limit.

<The content rate of each component in the photosensitive coloring composition>

Although the content rate of (a) coloring agent in the photosensitive coloring composition of this invention is not specifically limited, 5 mass % or more is preferable in total solid, 10 mass % or more is more preferable, 20 mass % or more is still more preferable, , more preferably 30 mass% or more, particularly preferably 35 mass% or more, more preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, and still more preferably 45 mass% or less. % or less is particularly preferred. For example, 5 mass % - 70 mass % are preferable, 10 mass % - 70 mass % are more preferable, 20 mass % - 60 mass % are still more preferable, 20 mass % - 50 mass % are still more preferable and 20 mass % - 45 mass % are especially preferable. There exists a tendency for light-shielding property to be securable by setting it as more than the said lower limit. There exists a tendency for patternability to improve by using below the said upper limit.

When the photosensitive coloring composition contains an organic coloring pigment, the content rate is although it does not specifically limit, 5 mass % or more is preferable in the total solid of the photosensitive coloring composition, 20 mass % or more is more preferable, 30 mass % or more More preferably, 35 mass % or more is especially preferable, 70 mass % or less is preferable, 60 mass % or less is more preferable, 50 mass % or less is especially preferable. For example, 5 mass % - 70 mass % are preferable, 20 mass % - 70 mass % are more preferable, 20 mass % - 60 mass % are still more preferable, 20 mass % - 50 mass % are especially preferable . There exists a tendency for light-shielding property to become high, suppressing the loss of the ultraviolet light required for hardening by setting it as more than the said lower limit. There exists a tendency for NMP tolerance to become favorable by setting it as below the said upper limit.

(a) When the colorant contains a red pigment and/or an orange pigment, the total content of the red pigment and the orange pigment is not particularly limited, but in (a) the colorant is preferably 5 mass% or more, and 8 mass% or more This is more preferable, 10 mass % or more is still more preferable, 12 mass % or more is especially preferable, and 40 mass % or less is preferable, 30 mass % or less is more preferable, 20 mass % or less is especially preferable. . For example, 5 mass % - 40 mass % are preferable, 8 mass % - 40 mass % are more preferable, 10 mass % - 30 mass % are still more preferable, 12 mass % - 20 mass % are especially preferable . There exists a tendency which can be set as the color tone close|similar to black by setting it as more than the said lower limit. There exists a tendency to become high sensitivity by using below the said upper limit.

(a) When the colorant contains a blue pigment and/or a purple pigment, the total content of the blue pigment and the purple pigment is not particularly limited, but in (a) the colorant is preferably 30 mass% or more, and 50 mass% or more More preferably, 70 mass % or more is more preferable, 80 mass % or more is especially preferable, 95 mass % or less is preferable, 92 mass % or less is more preferable, and 90 mass % or less is especially preferable. . For example, 30 mass % - 95 mass % are preferable, 50 mass % - 95 mass % are more preferable, 70 mass % - 92 mass % are still more preferable, 80 mass % - 90 mass % are especially preferable . There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. There exists a tendency for NMP tolerance to become favorable by setting it as below the said upper limit.

When the photosensitive coloring composition contains a black pigment, the content rate is not specifically limited, 2 mass % or more is preferable in the total solid of the photosensitive coloring composition, 3 mass % or more is more preferable, 5 mass % or more is further Preferably, 10 mass % or more is more preferable, 20 mass % or more is especially preferable, and 60 mass % or less is preferable, 50 mass % or less is more preferable, and 40 mass % or less is especially preferable. For example, 2 mass % - 60 mass % are preferable, 5 mass % - 60 mass % are more preferable, 10 mass % - 50 mass % are still more preferable, 20 mass % - 40 mass % are especially preferable . There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. There exists a tendency for NMP tolerance to become favorable by setting it as below the said upper limit.

Moreover, when the photosensitive coloring composition contains an organic black pigment, the content rate is although it does not specifically limit, 2 mass % or more is preferable in the total solid of the photosensitive coloring composition, 3 mass % or more is more preferable, 5 mass % More preferably, 10 mass % or more is still more preferable, 20 mass % or more is particularly preferable, and 60 mass % or less is preferable, 50 mass % or less is more preferable, and 40 mass % or less is especially desirable. For example, 2 mass % - 60 mass % are preferable, 5 mass % - 60 mass % are more preferable, 10 mass % - 50 mass % are still more preferable, 20 mass % - 40 mass % are especially preferable . There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. There exists a tendency for NMP tolerance to become favorable by setting it as below the said upper limit.

(a) When the colorant contains an organic black pigment, the content is not particularly limited, but in (a) the colorant is preferably 5 mass % or more, more preferably 10 mass % or more, and furthermore 15 mass % or more It is preferable, and 20 mass % or more is especially preferable, 100 mass % or less is preferable, 80 mass % or less is more preferable, and 70 mass % or less is especially preferable. For example, 5 mass % - 100 mass % are preferable, 10 mass % - 100 mass % are more preferable, 15 mass % - 80 mass % are still more preferable, 20 mass % - 70 mass % are especially preferable . There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. There exists a tendency for NMP tolerance to become favorable by setting it as below the said upper limit.

Moreover, when the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content rate is although it does not specifically limit, 5 mass % or more is preferable in (a) coloring agent, 10 mass % or more is more preferable, 15 mass % or more % or more is more preferable, and 60 mass % or less is preferable, 50 mass % or less is more preferable, and 40 mass % or less is especially preferable. For example, 5 mass % - 60 mass % are preferable, 10 mass % - 50 mass % are more preferable, and 15 mass % - 40 mass % are still more preferable. There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. There exists a tendency for NMP tolerance to become favorable by setting it as below the said upper limit.

Further, when (a) the colorant contains an organic color pigment and a black pigment, the total content is not particularly limited, but in (a) the colorant is preferably 5 mass% or more, more preferably 10 mass% or more, , 15 mass % or more is more preferable, 100 mass % or less is preferable, 70 mass % or less is more preferable, 50 mass % or less is especially preferable. For example, 5 mass % - 100 mass % are preferable, 10 mass % - 70 mass % are more preferable, 15 mass % - 50 mass % are still more preferable. There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. There exists a tendency for NMP tolerance to become favorable by setting it as below the said upper limit.

(b) Although the content rate of alkali-soluble resin is not specifically limited, Usually 5 mass % or more in the total solid of the photosensitive coloring composition of this invention, Preferably it is 10 mass % or more, More preferably, it is 20 mass % or more, More preferably Preferably it is 30 mass % or more, Especially preferably 35 mass % or more, Usually 85 mass % or less, Preferably 80 mass % or less, More preferably, it is 70 mass % or less, More preferably, it is 60 mass % or less. More preferably, it is 50 mass % or less, Especially preferably, it is 45 mass % or less. For example, 5 mass % - 85 mass % are preferable, 5 mass % - 80 mass % are more preferable, 10 mass % - 70 mass % are still more preferable, 20 mass % - 60 mass % are still more preferable and 30 mass % - 50 mass % are especially preferable, and 35 mass % - 45 mass % are especially preferable. By using more than the said lower limit, there exists a tendency which suppresses the fall of the solubility with respect to the developing solution of an unexposed part, and can suppress image development. By carrying out below the said upper limit, there exists a tendency which can maintain appropriate sensitivity, can suppress dissolution by the developing solution of an exposure part, and can suppress the sharpness of a pattern, and the fall of adhesiveness.

(b1) Although the content rate of the epoxy (meth)acrylate-type resin is not specifically limited, Usually 5 mass % or more in the total solid of the photosensitive coloring composition of this invention, Preferably it is 10 mass % or more, More preferably, 15 mass % or more, more preferably 20 mass% or more, and usually 50 mass% or less, preferably 40 mass% or less, more preferably 30 mass% or less. For example, 5 mass % - 50 mass % are preferable, 10 mass % - 50 mass % are more preferable, 15 mass % - 40 mass % are still more preferable, 20 mass % - 30 mass % are especially preferable . By setting it as more than the said lower limit, there exists a tendency which the solubility with respect to the developing solution of an unexposed part can be ensured. By setting it as below the said upper limit, there exists a tendency which can maintain appropriate sensitivity, can suppress dissolution by the developing solution of an exposure part, and can suppress the sharpness of a pattern, and the fall of adhesiveness.

(b) Although the content rate of (b1) epoxy (meth)acrylate-type resin contained in alkali-soluble resin is not specifically limited, Usually 20 mass % or more, Preferably 30 mass % or more, More preferably, 40 mass % or more, usually 90 mass % or less, Preferably it is 85 mass % or less, More preferably, it is 80 mass % or less. For example, 20 mass % - 90 mass % are preferable, 30 mass % - 85 mass % are more preferable, 40 mass % - 80 mass % are still more preferable. By setting it as more than the said lower limit, there exists a tendency which the solubility with respect to the developing solution of an unexposed part can be ensured. By setting it as below the said upper limit, there exists a tendency which can maintain appropriate sensitivity, can suppress dissolution by the developing solution of an exposure part, and can suppress the sharpness of a pattern, and the fall of adhesiveness.

(c) Although the content rate of a photoinitiator is not specifically limited, It is 0.1 mass % or more normally in the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.5 mass % or more, More preferably, it is 1 mass % or more, More preferably Preferably it is 2 mass % or more, More preferably, it is 3 mass % or more, Usually 15 mass % or less, Preferably it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 6 mass % or less. . For example, 0.1 mass % - 15 mass % are preferable, 0.5 mass % - 15 mass % are more preferable, 1 mass % - 10 mass % are still more preferable, 2 mass % - 8 mass % are still more preferable and 3 mass % - 6 mass % are especially preferable. There exists a tendency which a sensitivity fall can be suppressed by setting it as more than the said lower limit. By carrying out below the said upper limit, there exists a tendency which suppresses the fall of the solubility with respect to the developing solution of an unexposed part, and can suppress image development.

(c) When a polymerization accelerator is used together with a photoinitiator, the content rate of the polymerization accelerator is not particularly limited, but preferably 0.05 mass% or more, usually 10 mass% or less, in the total solid content of the photosensitive coloring composition of the present invention; Preferably it is 5 mass % or less. Moreover, it is preferable to use a polymerization accelerator in the ratio of 0.1-50 mass parts normally with respect to 100 mass parts of (c) photoinitiators, and especially 0.1-20 mass parts. By making the content rate of a polymerization accelerator more than the said lower limit, there exists a tendency which can suppress the fall of the sensitivity with respect to an exposure light beam. By carrying out below the said upper limit, there exists a tendency which suppresses the fall of the solubility with respect to the developing solution of an unexposed part, and can suppress image development.

Moreover, (c) When using a sensitizing dye with a photoinitiator, the content rate is although it does not specifically limit, From a viewpoint of a sensitivity, it is 20 mass % or less normally in the total solid in the photosensitive coloring composition, Preferably 15 mass % or less. , More preferably, it is 10 mass % or less.

(d) The content rate of the ethylenically unsaturated compound is not particularly limited, but is usually 1 mass % or more, preferably 5 mass % or more, more preferably 10 mass % or more, in the total solid content of the photosensitive coloring composition of the present invention, Moreover, it is 30 mass % or less normally, Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less. For example, 1 mass % - 30 mass % are preferable, 5 mass % - 20 mass % are more preferable, 10 mass % - 15 mass % are still more preferable. By setting it as more than the said lower limit, there exists a tendency which can maintain an appropriate sensitivity, can suppress dissolution by the developing solution of an exposure part, and can suppress the sharpness of a pattern, and the fall of adhesiveness. By setting it below the said upper limit, it suppresses that the permeability of the developing solution with respect to an exposed part becomes high, and it exists in the tendency for it to become easy to obtain a favorable image.

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

(f) Although the content rate of a dispersing agent is not specifically limited, It is 1 mass % or more normally in the total solid of the photosensitive coloring composition, 3 mass % or more is preferable, 5 mass % or more is more preferable, and 30 mass % or less normally , 20 mass % or less is preferable, 15 mass % or less is more preferable, and 10 mass % or less is still more preferable. For example, 1 mass % - 30 mass % are preferable, 1 mass % - 20 mass % are more preferable, 3 mass % - 15 mass % are still more preferable, 5 mass % - 10 mass % are especially preferable . By using more than the said lower limit, there exists a tendency for sufficient dispersibility to be easy to be obtained. Since the ratio of other components can be relatively maintained at a fixed level or more by setting it as below the said upper limit, there exists a tendency which can suppress that a sensitivity, plate-making property, etc. fall.

Although the content rate of a dispersing agent (f1) is not specifically limited, In total solid of the photosensitive coloring composition, it is 1 mass % or more normally, 3 mass % or more is preferable, 5 mass % or more is more preferable, and 30 mass % or less normally , 20 mass % or less is preferable, 15 mass % or less is more preferable, and 10 mass % or less is still more preferable. For example, 1 mass % - 30 mass % are preferable, 1 mass % - 20 mass % are more preferable, 3 mass % - 15 mass % are still more preferable, 5 mass % - 10 mass % are especially preferable . By using more than the said lower limit, there exists a tendency for dispersibility to become favorable. There exists a tendency for the voltage retention after ultraviolet irradiation to become high by setting it as below the said upper limit.

Although the content rate of the dispersing agent (f1) is not specifically limited, (f) In a dispersing agent, it is 10 mass % or more normally, 40 mass % or more is preferable, 60 mass % or more is more preferable, 80 mass % or more is still more preferable, , and is usually 100% by mass or less. By using more than the said lower limit, there exists a tendency for NMP tolerance to improve.

Moreover, the content ratio of (f) dispersing agent with respect to (a) 100 mass parts of coloring agents is 5 mass parts or more, 10 mass parts or more are more preferable normally, 15 mass parts or more are still more preferable, Usually 50 mass parts or less, It is especially preferable that it is 30 mass parts or less. For example, 5 mass parts - 50 mass parts are preferable, 10 mass parts - 50 mass parts are more preferable, 15 mass parts - 30 mass parts are still more preferable. By using more than the said lower limit, there exists a tendency for sufficient dispersibility to be easy to be obtained. There exists a tendency that it can suppress that a sensitivity, plate-making property, etc. fall because the ratio of another component decreases relatively by setting it as below the said upper limit.

On the other hand, as for the content rate of (b) alkali-soluble resin with respect to 100 mass parts of (d) ethylenically unsaturated compounds, 80 mass parts or more and 100 mass parts or more are preferable normally, 150 mass parts or more are more preferable, 200 mass Parts by weight or more are more preferable, and 250 parts by mass or more is particularly preferable, and usually 700 parts by mass or less and 500 parts by mass or less are preferable, more preferably 400 parts by mass or less, and still more preferably 300 parts by mass or less. For example, 80 mass parts - 700 mass parts are preferable, 100 mass parts - 700 mass parts are more preferable, 150 mass parts - 500 mass parts are still more preferable, 200 mass parts - 400 mass parts are still more preferable, 250 mass parts Part to 300 parts by mass is particularly preferable. By setting it as more than the said lower limit, there exists a tendency to become an appropriate dissolution development state without peeling etc. There exists a tendency for the suitable dissolution time to be obtained with respect to a developing solution by using below the said upper limit.

Although the content rate is not specifically limited when using an adhesion improving agent, It is 0.1-5 mass % normally in the total solid of the photosensitive coloring composition, Preferably it is 0.2-3 mass %, More preferably, it is 0.4-2 mass %. There exists a tendency which the adhesive improvement effect can fully be acquired by using more than the said lower limit. There exists a tendency which can suppress that a sensitivity falls or a residue remains after image development and becomes a defect by using below the said upper limit.

When using surfactant, the content rate is although it does not specifically limit, Usually 0.001-10 mass % in total solid of the photosensitive coloring composition, Preferably it is 0.005-1 mass %, More preferably, 0.01-0.5 mass %, most Preferably it is 0.03-0.3 mass %. There exists a tendency for the smoothness and uniformity of a coating film to express easily by setting it as more than the said lower limit. By setting it as below the said upper limit, the smoothness and uniformity of a coating film are easy to express, and there exists a tendency which the deterioration of other characteristics can also be suppressed.

<Physical properties of the photosensitive coloring composition>

As for the photosensitive coloring composition of this invention, the optical density (OD) per 1 micrometer of film thickness of the coating film is 0.5 or more. 0.7 or more are more preferable, 1.0 or more are still more preferable, 1.3 or more are still more preferable, 1.5 or more are especially preferable, and are usually 4.0 or less, 3.0 or less are preferable, and 2.0 or less are more preferable. For example, 0.5-4.0 are preferable, 0.7-4.0 are more preferable, 1.0-3.0 are still more preferable, 1.3-3.0 are still more preferable, 1.5-2.0 are especially preferable. By setting it as more than the said lower limit, there exists a tendency for sufficient light-shielding property to be acquired. There exists a tendency for voltage retention and NMP tolerance to become favorable by setting it as below the said upper limit.

The optical density (OD) per 1 µm thickness of the coating film may be measured using a cured coating film of the photosensitive coloring composition of the present invention, and can be measured using a coating film heated and cured at 230°C for 20 minutes.

The optical density refers to the transmission optical density in which the spectral sensitivity characteristic of the light receiving unit is expressed by ISO visual density in the ISO 5-3 standard. Usually, as a light source, the A light source prescribed|regulated by CIE (International Illumination Commission) is used. As a measuring instrument which can be used for the measurement of transmitted optical density, X-Rite 361T(V) by Sakata Ing's Engineering Co., Ltd. is mentioned, for example.

<The manufacturing method of the photosensitive coloring composition>

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

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

Dispersion treatment is usually preferably carried out in a system in which (a) a colorant, (e) a solvent, and (f) a dispersant, and (b) some or all of the alkali-soluble resin are used in combination (hereinafter, obtained by dispersion treatment) The composition is sometimes referred to as "pigment dispersion"). In particular (f), the use of a polymer dispersing agent as the dispersing agent is preferable because the resulting pigment dispersion and the photosensitive coloring composition are suppressed from thickening over time, ie, 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, even if it is set as the content rate of each colorant of the (a) coloring agent in a pigment dispersion liquid, what was described as a content rate in the photosensitive coloring composition is employable preferably.

When a dispersion process is performed with respect to the liquid containing all the components mix|blended with the photosensitive coloring composition, a highly reactive component may be modified|denatured because of the heat generation|occurrence|production at the time of a dispersion process. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersing agent.

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 from 0°C to 100°C, preferably from room temperature to 80°C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like. Controlling glossiness of a pigment dispersion liquid is a dispersion|distribution standard so that the 20 degree|times specular glossiness (JISZ8741) of the photosensitive coloring composition may become the range of 50-300. When the glossiness of the photosensitive coloring composition is low, dispersion treatment is not enough, and coarse pigment (color material) particles remain in many cases, and developability, adhesiveness, resolution, etc. may become inadequate. If the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, and thus dispersion stability tends to be inhibited on the contrary.

The dispersed particle diameter of the pigment dispersed in the pigment dispersion is usually 0.03 to 0.3 mu m, and can be measured by a dynamic light scattering method.

Next, the pigment dispersion liquid 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 or dispersion liquid. In the manufacturing process of the photosensitive coloring composition, since fine dust may mix in a liquid, it is preferable to filter the obtained photosensitive coloring composition with a filter etc.

[Pigment Dispersion for Image Display]

The pigment dispersion for an image display device of the present invention contains (a) a colorant, (e) a solvent, and (f) a dispersing agent, and in particular, the (a) colorant contains a black pigment, and the (f) ) The dispersing agent contains a dispersing agent (f1).

In the pigment dispersion liquid for an image display device of the present invention, as (a) colorant, (e) solvent, and (f) dispersant, those exemplified as the same item in the photosensitive coloring composition of the present invention are preferably employed can do. Similarly, also as a black pigment and a dispersing agent (f1) in the pigment dispersion liquid for image display devices of this invention, what was illustrated as the same item in the photosensitive coloring composition of this invention can be employ|adopted preferably.

The pigment dispersion for image display devices of this invention WHEREIN: Although the content rate of (a) coloring agent is not specifically limited, 30 mass % or more is preferable in total solid, 50 mass % or more is more preferable, 60 mass % or more This is still more preferable, and 80 mass % or less is preferable, 75 mass % or less is more preferable, and 70 mass % or less is still more preferable. For example, 30 mass % - 80 mass % are preferable, 50 mass % - 75 mass % are more preferable, 60 mass % - 70 mass % are still more preferable. There exists a tendency for the voltage retention after ultraviolet irradiation and NMP tolerance to become favorable by setting it as more than the said lower limit. There exists a tendency for dispersibility to become favorable by using below the said upper limit.

The pigment dispersion for image display devices of the present invention WHEREIN: Although the content rate of a black pigment is not specifically limited, In total solid, 30 mass % or more is preferable, 50 mass % or more is more preferable, 60 mass % or more is further It is preferable, and 80 mass % or more is especially preferable, 75 mass % or less is preferable, and 70 mass % or less is more preferable. For example, 30 mass % - 80 mass % are preferable, 50 mass % - 75 mass % are more preferable, 60 mass % - 70 mass % are still more preferable. There exists a tendency for the voltage retention after ultraviolet irradiation and NMP tolerance to become favorable by setting it as more than the said lower limit. There exists a tendency for dispersibility to become favorable as it is below the said upper limit.

The pigment dispersion liquid for image display devices of this invention WHEREIN: It is preferable from a light-shielding viewpoint at the time of using as a photosensitive coloring composition that the organic black pigment represented by the above-mentioned structural formula (1) is included among black pigments.

The content ratio of the organic black pigment of the structural formula (1) to the (a) colorant is preferably 10 mass% or more, more preferably 40 mass% or more, and still more preferably 70 mass% or more, in the total (a) colorant. and 90 mass % or more is especially preferable, and 98 mass % or more is especially more preferable.

The pigment dispersion for image display devices of this invention WHEREIN: (f) Although the content rate of a dispersing agent is not specifically limited, 1 mass % or more is preferable in total solid, 5 mass % or more is more preferable, 8 mass % or more This is more preferable, 10 mass % or more is especially preferable, 35 mass % or less is preferable, 30 mass % or less is more preferable, 20 mass % or less is still more preferable, 15 mass % or less is especially preferable. . For example, 1 mass % - 35 mass % are preferable, 5 mass % - 30 mass % are more preferable, 8 mass % - 20 mass % are still more preferable, 10 mass % - 15 mass % are especially preferable. . There exists a tendency for dispersibility to become favorable by setting it as more than the said lower limit. There exists a tendency for the voltage retention after ultraviolet irradiation and NMP tolerance to become favorable by using below the said upper limit.

In the pigment dispersion for an image display device of the present invention, the content of the dispersant (f1) is not particularly limited, but is preferably 5 mass% or more, more preferably 8 mass% or more, and more preferably 10 mass% or more, in the total solid content. This is still more preferable, and 35 mass % or less is preferable, 30 mass % or less is more preferable, 20 mass % or less is still more preferable, and 15 mass % or less is especially preferable. For example, 5 mass % - 35 mass % are preferable, 5 mass % - 30 mass % are more preferable, 8 mass % - 20 mass % are still more preferable, 10 mass % - 15 mass % are especially preferable. . There exists a tendency for dispersibility to become favorable by setting it as more than the said lower limit. There exists a tendency for the voltage retention after ultraviolet irradiation and NMP tolerance to become favorable by using below the said upper limit.

Although the content rate of the dispersing agent (f1) is not specifically limited, (f) In a dispersing agent, it is 10 mass % or more normally, 40 mass % or more is preferable, 60 mass % or more is more preferable, 80 mass % or more is still more preferable, , and is usually 100% by mass or less. By using more than the said lower limit, there exists a tendency for NMP tolerance to improve.

Moreover, in the pigment dispersion liquid for image display devices of this invention, the content rate of total solid is 10 mass % or more normally by using (e) solvent, Preferably it is 15 mass % or more, More preferably, 20 mass % or more. , and is usually 40 mass% or less, preferably 35 mass% or less, and more preferably 30 mass% or less. Preferably it is 10 mass % - 40 mass %, More preferably, it is 15 mass % - 35 mass %, More preferably, it prepares so that it may become 20 mass % - 30 mass %.

[Cured material]

By hardening the photosensitive coloring composition of this invention, the hardened|cured material of this invention can be obtained. The hardened|cured material of this invention can be used suitably as a colored spacer.

Moreover, the hardened|cured material formed by hardening|curing the photosensitive coloring composition of this invention can be used suitably as a partition.

[Colored Spacer]

Next, the colored spacer using the photosensitive coloring composition of this invention is demonstrated according to the manufacturing method.

(1) support

As a support body for forming a colored spacer, as long as 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, thermoplastic resins, such as polycarbonate, polymethylmethacrylate, polysulfone A sheet, an epoxy resin, an unsaturated polyester resin, a thermosetting resin sheet, such as a poly(meth)acrylic-type resin, and various glass are mentioned. Especially, 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. Other than the transparent substrate, it can also be formed on the TFT array.

The support may be subjected to, if necessary, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as a silane coupling agent and urethane resin, if necessary in order to improve 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 is used for the same use as the well-known photosensitive coloring composition for color filters, Hereinafter, about the case used as a coloring spacer (black photospacer), the black photospacer using the photosensitive coloring composition of this invention. It will be described according to a specific example of the formation method of

Usually, on the board|substrate in which a black photospacer should be formed, the photosensitive coloring composition is supplied in the form of a film|membrane or a pattern by methods, such as application|coating, 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 black photospacer is formed on a board|substrate 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 board|substrate. 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, and the spray coat method. Moreover, you may supply in the form of a pattern by the inkjet method or the printing method, for example. Especially, according to the die coating method, the usage-amount of a coating liquid is significantly reduced, and there is no influence of mist etc. adhering when the spin coating method is used, and it is preferable from a general viewpoint, such as suppressing the generation|occurrence|production of a foreign material.

Although the application amount varies depending on the application, for example, in the case of a black photospacer, as a dry film thickness, it is usually 0.5 µm to 10 µm, preferably 1 µm to 9 µm, particularly preferably 1 µm to 7 µm. is applied It is important that the dry film thickness or the height of the finally formed spacer is uniform across the substrate. When the variation is small, it is possible to suppress the non-uniformity defect that occurs in the liquid crystal panel.

When using the photosensitive coloring composition of this invention to collectively form black photo-spacers from which height differs by the photolithographic method, the height of the finally formed black photo-spacers becomes different.

In addition, as a board|substrate, well-known board|substrates, such as a glass substrate, can be used. The substrate surface is preferably flat.

[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. You may combine the reduced-pressure drying method which dries in a pressure reduction chamber without raising a temperature.

Drying conditions can be suitably selected according to the kind of solvent component, the performance of the dryer to be used, etc. Drying time is usually selected from the range of 15 seconds - 5 minutes at the temperature of 40 degreeC - 130 degreeC according to the kind of solvent component, the performance of the dryer to be used, etc., Preferably at the temperature of 50 degreeC - 110 degreeC It is selected from the range of 30 seconds - 3 minutes.

[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 the 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 light through the exposure mask It can also be done by a method of projecting It is also possible by the scanning exposure method by the laser beam which does not use a mask pattern. If necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer by oxygen, exposure may be carried out in a deoxidized atmosphere or after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer. .

As a preferred aspect of the present invention, when black photospacers having different heights are simultaneously formed by photolithography, for example, the light-shielding portion (light transmittance 0%) and the plurality of openings have the highest average light transmittance. An exposure mask having an opening having a small average light transmittance (intermediate transmission opening) with respect to the opening (completely transmitting opening) is used. According to this method, the difference in the residual 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 is known in which the intermediate transmission opening is manufactured by, for example, a matrix-like light-shielding pattern having a light-shielding unit of minute polygons. Moreover, as an absorber, the method of manufacturing by controlling the light transmittance with the film|membrane of a chromium type, a molybdenum type|system|group, a tungsten type, and a silicon type material is known, for example.

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 an excimer laser, a nitrogen laser, a helium cadmium laser, a blue-violet semiconductor laser, and a near-infrared semiconductor laser. In the case of irradiating and using light of a specific wavelength, an optical filter may be used.

As an optical filter, for example, it is a thin film, and the type which can control the light transmittance in an exposure wavelength may be sufficient as a material in that case, For example, Cr compound (Oxide of Cr, nitride, oxynitride, fluoride, etc.) , MoSi, Si, W, and Al 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, and usually 300 mJ/cm 2 or less, preferably 200 mJ/cm 2 or less, more preferably It is preferably 150 mJ/cm 2 or less.

In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 µm or more, preferably 50 µm or more, more preferably 75 µm or more, and usually 500 µm or less, preferably 400 µm or less, More preferably, 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 an organic solvent. The aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

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. , sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, etc. inorganic alkaline compounds, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or and 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. These organic solvents may use 2 or more types together. Moreover, an organic solvent may be used independently and may be used together with the aqueous solution of water or an alkaline compound.

There is no restriction|limiting in particular on the conditions of developing treatment, Usually, the developing temperature is 10-50 degreeC, Preferably it is 15-45 degreeC, More preferably, it is 20-40 degreeC. The developing method can be based on the immersion developing method, the spray developing method, the brush developing method, and the ultrasonic developing method, for example.

[5] Addition exposure and heat curing treatment

If necessary, the substrate after image development may be subjected to additional exposure by the same method as the above exposure method, or may be subjected to a thermosetting treatment. The thermosetting treatment condition is that the temperature is 100°C to 280°C, preferably 150°C to 250°C, and the time is 5 minutes to 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 this is applied, the photosensitive coloring composition of the present invention is, in particular, a black photo in which the height of the spacer and the sub-spacer differs by the photolithography method. It is useful for simultaneously forming spacers. The height of the spacer is usually about 2 to 7 µm, and the height of the subspacer is usually about 0.2 to 1.5 µm lower than that of the spacer.

In addition, the optical density (OD) per 1 µm of the colored spacer of the present invention is preferably 0.7 or more, more preferably 1.2 or more, still more preferably 1.5 or more, particularly preferably 1.8 or more, from the viewpoint of light-shielding property, , usually 4.0 or less, preferably 3.0 or less. For example, 0.7-4.0 are preferable, 1.2-4.0 are more preferable, 1.5-3.0 are still more preferable, 1.8-3.0 are especially preferable. Here, the optical density (OD) is a value measured by the method mentioned later.

[septum]

The photosensitive coloring composition of this invention can be used suitably in order to form the partition for partitioning the barrier rib, especially the organic layer of an organic electroluminescent element. As an organic layer used for an organic electroluminescent element, the organic layer used for the hole injection layer described in Unexamined-Japanese-Patent No. 2016-165396, a hole transport layer, or a hole transport layer on a hole injection layer is mentioned, for example.

The partition using the photosensitive coloring composition of this invention is demonstrated according to the manufacturing method.

(1) support

As a support body and board|substrate for forming a partition, the thing similar to the support body and board|substrate for forming the above-mentioned colored spacer and board|substrate can be used.

(2) bulkhead

Hereinafter, the case where it is used as a partition is demonstrated according to the specific example of the formation method of the partition using the photosensitive coloring composition of this invention.

Usually, on the board|substrate which a partition should form, the photosensitive coloring composition is supplied in the form of a film|membrane or a pattern by methods, such as application|coating, 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 barrier rib is formed on a board|substrate by performing additional exposure or a thermosetting process as needed.

(3) formation of bulkheads

In the method for forming a barrier rib using the photosensitive coloring composition of the present invention, the method for supplying the photosensitive coloring composition to the substrate, the drying method, the exposure method, the developing method, the additional exposure method, and the specific method of the thermosetting treatment are the above-mentioned coloring The same method as the formation of the spacer can be employed.

Although the size, shape, etc. in the case of using this invention as a partition are suitably adjusted according to the specification of the organic electroluminescent element to which this is applied, etc., the height of the partition formed from the photosensitive coloring composition of this invention is about 0.5-10 micrometers normally.

Moreover, from a light-shielding viewpoint, 0.7 or more are preferable, as for the optical density (OD) per 1 micrometer as a partition of this invention, 1.2 or more are more preferable, 1.5 or more are still more preferable, and 1.8 or more are especially preferable. Moreover, it is 4.0 or less normally, and it is preferable that it is 3.0 or less. For example, 0.7-4.0 are preferable, 1.2-4.0 are more preferable, 1.5-3.0 are still more preferable, 1.8-3.0 are especially preferable. Here, the optical density (OD) is a value measured by the method mentioned later.

[Organic electroluminescent device]

The organic electroluminescent element of this invention is equipped with the hardened|cured material comprised from the photosensitive coloring composition mentioned above, for example, a partition.

For example, various organic electroluminescent elements are manufactured using the board|substrate provided with the barrier rib pattern manufactured by the above-mentioned method. Although the method of forming an organic electroluminescent element is not specifically limited, Preferably, after forming the pattern of a partition on a board|substrate by the above-mentioned method, a functional material is sublimed in a vacuum state, and is surrounded by the partition on a board|substrate. An organic electroluminescent element is manufactured by forming organic layers, such as a pixel, by the vapor deposition method which deposits and forms into a film in an area|region, or a wet process, such as a casting method, a spin coating method, and an inkjet printing method.

As a type of an organic electroluminescent element, a bottom emission type and a top emission type are mentioned.

In the bottom emission type, for example, a barrier rib is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated on an opening surrounded by the barrier rib. On the other hand, in the top emission type, for example, a barrier rib is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the barrier rib.

Moreover, as a light emitting layer, the organic electroluminescent layer described in Unexamined-Japanese-Patent No. 2009-146691 and Unexamined-Japanese-Patent No. 5734681 is mentioned. Moreover, you may use the quantum dot described in Unexamined-Japanese-Patent No. 5653387 and Unexamined-Japanese-Patent No. 5653101.

The layer configuration is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may have a laminate configuration of two or more layers from the viewpoint of luminous efficiency. Although the thickness of each layer is not specifically limited, From a viewpoint of luminous efficiency and a brightness|luminance, it is 1-500 nm normally.

An organic electroluminescent element may divide each RGB color for every opening part, and may form it, and may laminate|stack two or more colors in one opening part. The organic electroluminescent element may be equipped with the sealing layer from a viewpoint of a reliability improvement. The encapsulation layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent device, thereby reducing luminous efficiency. The organic electroluminescent element may be equipped with the low reflection film at the interface with air from a viewpoint of the improvement of light extraction efficiency. By disposing the low-reflection film at the interface between the air and the element, it can be expected that the refractive index gap is reduced and reflection at the interface is suppressed. For such a low-reflection film, for example, a technology of a moth-eye structure or an ultra-multilayer film may be applied.

When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light of the light emitting layer of one pixel from leaking to another pixel, and when an electrode etc. are metal, the image quality accompanying reflection of external light Since it is necessary to prevent the fall of the light-shielding property to the partition which comprises an organic electroluminescent element, it is preferable.

Moreover, in an organic electroluminescent element, since it is necessary to provide an electrode to the upper surface and the lower surface of a barrier rib, it is preferable from an insulating viewpoint that a barrier rib has a high resistance and low dielectric constant. Therefore, when using a coloring agent in order to provide light-shielding property to a partition, it is preferable to use the said organic pigment which is high resistance and low dielectric constant.

[Image display device]

The image display device of this invention contains the hardened|cured material of this invention.

For example, an alignment film is formed on a liquid crystal driving substrate (array substrate) having a colored spacer formed of the photosensitive coloring composition of the present invention, and a liquid crystal cell is formed by bonding to a counter electrode substrate, and in the formed liquid crystal cell By injecting a liquid crystal, image display devices, such as a liquid crystal display device containing the hardened|cured material of this invention, can be manufactured.

In addition, by providing a colored spacer formed of the photosensitive coloring composition of the present invention on the opposite electrode substrate side, bonding with a liquid crystal driving substrate (array substrate) to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell, the method of the present invention Image display devices, such as a liquid crystal display device containing cargo, can be manufactured.

As described in Unexamined-Japanese-Patent No. 2014-215614, liquid-crystal orientation can be improved by irradiating an ultraviolet-ray after injecting a liquid crystal into a liquid crystal cell using a specific orientation substance.

As an image display device of this invention, the organic electroluminescent display which has a partition containing the hardened|cured material of this invention, and an organic electroluminescent element is also mentioned.

The organic EL display device is not particularly limited as to the form or structure of the image display device as long as it contains the above-described organic EL device, for example, according to a conventional method using an active driving type organic EL device. can be assembled For example, it can form by the method described in "Organic EL display" (Oum Corporation, August 20, 2004 publication, Tokito Shizuo, Adachi Chihaya, Murata Hideyuki). For example, an image may be displayed by combining an organic electroluminescent element emitting white light and a color filter, or an image may be displayed by combining an organic electroluminescent element having different emission colors such as RGB.

[light]

The organic electroluminescent device including the cured product of the present invention may be used for lighting. There is no particular limitation on the type or structure of lighting, and it can be assembled according to a conventional method using an organic electroluminescent device including the cured product of the present invention. As an organic electroluminescent element, it is good also as a simple matrix driving system, and good also as an active matrix driving system.

In order for illumination to emit white light, you may use the organic electroluminescent element which emits white light. Moreover, organic electroluminescent elements with different emission colors may be combined and each color may be mixed so that it may be comprised so that it may become white, or a color mixing function may be provided so that a color mixing ratio can be adjusted.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless departing from the gist thereof.

Components of the pigment dispersion and photosensitive coloring composition used in the following Examples and Comparative Examples, and their evaluation methods are as follows.

<Alkali-soluble resin-I>

It stirred, replacing 145 mass parts of propylene glycol monomethyl ether acetate (PGMEA) with nitrogen, and it heated up at 120 degreeC. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are added dropwise thereto, followed by 2,2'-azobis 8.47 mass parts of -2-methylbutyronitrile were dripped over 3 hours, and stirring was continued at 90 degreeC for 2 hours. Next, the inside of reaction container was changed to air substitution, 0.7 mass parts of trisdimethylaminomethylphenol and 0.12 mass parts of hydroquinone were thrown into 43.2 mass parts of acrylic acid, and reaction was continued at 100 degreeC for 12 hours. Then, 56.2 mass parts of tetrahydrophthalic anhydride (THPA) and 0.7 mass parts of triethylamine were added, and it was made to react at 100 degreeC for 3.5 hours. The weight average molecular weight Mw of the obtained alkali-soluble resin-I measured by GPC was 8400, and the acid value was 80 mgKOH/g.

<Alkali-soluble resin-II>

Nippon Kayaku Co., Ltd. "XD1000" (polyglycidyl ether of dicyclopentadiene phenol polymer, epoxy equivalent 252) 300 parts by mass, 87 parts by mass of acrylic acid, 0.2 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine parts and 255 parts by mass of propylene glycol monomethyl ether acetate were poured into the reaction vessel, and stirred at 100°C until the acid value became 3.0 mgKOH/g. Then, 145 mass parts of tetrahydrophthalic anhydride was further added, and it was made to react at 120 degreeC for 4 hours. The weight average molecular weight Mw measured by GPC of the alkali-soluble resin-II obtained in this way was 2600, and the acid value was 106 mgKOH/g.

<Pigment-I>

C. I. Pigment Blue 60

<Pigment-II>

C. I. Pigment Orange 64

<Pigment-III>

C. I. Pigment Violet 29

<Pigment-IV>

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

[Formula 48]

<Dispersant-I>

A methacrylic A-B-A triblock copolymer comprising an A block including a repeating unit having a solvent-friendly group and a B block including a repeating unit having a pigment adsorbing group. It has the repeating unit of following formula (a) - (g). The amine titer is 48 mgKOH/g. The theoretical molecular weight is 8,300.

The content ratio of the repeating units of the following formulas (a) to (g) in all repeating units is (a) 40.4 mol% (26.6 mass%), (b) 13.7 mol% (12.8 mass%), (c) 9.3 mol% (12.1 mass%), (d) 7.7 mol% (8.9 mass%), (e) 2.7 mol% (4.9 mass%), (f) 17.0 mol% (17.6 mass%), (g) 9.2 mol % (17.1 mass%).

[Formula 49]

[Formula 50]

<Dispersant-II>

A dispersing agent "BYK-LPN6919" made by Bikchemi. A methacrylic A-B block copolymer comprising an A block including a repeating unit having a solvent-friendly group and a B block including a repeating unit having a pigment adsorbing group. It has repeating units of the following formulas (2a) and (3a). The amine value is 120 mgKOH/g and the acid value is 1 mgKOH/g or less.

The content ratio of the repeating unit of the following formula (2a) and the repeating unit of the following formula (3a) in all repeating units is 33.3 mol% and 6.7 mol%, respectively.

[Formula 51]

<Dispersant-III>

2.92 parts by mass of dispersant-II (solid content, PGMEA solution) and 0.35 parts by mass of phenylphosphonic acid were mixed, and the solid content of the stirred mixture was used as dispersant-III.

Dispersant-III is presumed to have repeating units of the following formulas (1a-1), (2a), and (3a). The content ratio of the repeating unit of the following formula (1a-1), the repeating unit of the following formula (2a), and the repeating unit of the following formula (3a) in all repeating units is 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively am.

[Formula 52]

<Dispersant-IV>

2.88 parts by mass of dispersant-II (solid content, PGMEA solution) and 0.38 parts by mass of benzenesulfonic acid monohydrate were mixed, and the solid content of the stirred mixture was used as dispersant-IV.

Dispersant-IV is presumed to have repeating units of the following formulas (1a-2), (2a), and (3a). The content ratio of the repeating unit of the following formula (1a-2), the repeating unit of the following formula (2a), and the repeating unit of the following formula (3a) in all repeating units is 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively am.

[Formula 53]

<Dispersant-V>

Dispersant-II was mixed with 2.85 parts by mass (solid content, PGMEA solution) and p-toluenesulfonic acid was mixed with 0.41 parts by mass, and the solid content of the stirred mixture was used as dispersant-V.

Dispersant-V is presumed to have repeating units of the following formulas (1a-3), (2a), and (3a). The content ratio of the repeating unit of the following formula (1a-3), the repeating unit of the following formula (2a), and the repeating unit of the following formula (3a) in all repeating units is 13.0 mol%, 20.3 mol%, and 6.7 mol%, respectively am.

[Formula 54]

<Dispersant-VI>

A methacrylic A-B diblock copolymer comprising an A block including a repeating unit having a solvent-friendly group and a B block including a repeating unit having a pigment adsorbing group. It has the repeating unit of following formula (h) - (n). The amine titer is 70 mgKOH/g.

The content ratio of the repeating units of the following formulas (h) to (n) in all repeating units is (h) 33.3 mol%, (i) 13.3 mol%), (j) 6.7 mol%, (k) 6.7 mol, respectively. %, (l) 6.7 mol%), (m) 22.2 mol%, and (n) 11.1 mol%.

[Formula 55]

[Formula 56]

<Dispersant-VII>

2.90 parts by mass of dispersant-II (solid content, PGMEA solution) and 0.37 parts by mass of methyl p-toluenesulfonate were mixed, and the solid content of the stirred mixture was used as dispersant-VII.

Dispersant-VII is presumed to have repeating units of the following formulas (1a-5), (2a), and (3a). The content ratio of the repeating unit of the following formula (1a-4), the repeating unit of the following formula (2a), and the repeating unit of the following formula (3a) in all repeating units is 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively am.

[Formula 57]

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxy-1-butanol

<Photoinitiator-I>

Oxime ester-based photopolymerization initiator having the following chemical structure

[Formula 58]

<Photoinitiator-II>

Oxime ester compound having the following chemical structure

(4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate methyl)

[Formula 59]

<Ethylenically Unsaturated Compound>

DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

<Surfactant>

Megapac F-559 manufactured by DIC

<Additives>

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

<Evaluation of viscosity>

The viscosity of the prepared pigment dispersion was measured with a RE-85L type viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23°C, 20 rpm).

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

The optical density per unit film thickness was measured in the following procedure.

First, the prepared photosensitive coloring composition was apply|coated to a glass substrate with a spin coater so that the film thickness after heat-hardening might be set to 3.0 micrometers, and after drying under reduced pressure for 1 minute, it was dried at 90 degreeC for 140 second on a hotplate. About the obtained coating film, it exposed, without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp having an intensity of 45 mW/cm 2 at a wavelength of 365 nm was used, and the exposure amount was 50 mJ/cm 2 . Then, the resist-coated board|substrate 1 was obtained by heat-hardening at 230 degreeC in oven for 20 minutes.

The optical density (OD value) of the obtained resist-coated substrate 1 was measured using a 361T(V) transmission densitometer manufactured by X-Rite (color temperature of the illumination light source: about 2850K (equivalent to CIE standard light source A)), and the spectral sensitivity characteristics of the light receiving part: ISO 5- ISO visual density in the 3 standard), and the film thickness was measured by a non-contact surface/layer cross-sectional shape measurement system VertScan(R) 2.0 manufactured by Ryoka Systems, and from the optical density (OD value) and the film thickness, The optical density (unit OD value) per unit film thickness (1 µm) was calculated. In addition, the OD value is a numerical value indicating light-shielding ability, and a larger numerical value indicates higher light-shielding property.

<Evaluation of voltage retention (VHR) and ion density>

Each photosensitive coloring composition was apply|coated on the electrode board|substrate in which the ITO film|membrane was formed in one side, and after vacuum-drying for 1 minute, it dried at 90 degreeC for 140 second on a hotplate. About the obtained coating film, image exposure was performed on exposure conditions of 50 mJ/cm<2> and an illumination intensity of 45 mW/cm<2> using a high-pressure mercury-vapor lamp. Next, after performing shower image development with a water pressure of 0.15 Mpa in 25 degreeC using the about 0.05 mass % potassium hydroxide aqueous solution at 25 degreeC, pure water stopped image development and rinsed with water spray. Shower image development time was adjusted between 10 to 20 second, and it was made into about 1.6 times the time (break time) for which the unexposed photosensitive coloring composition layer is dissolved and removed. Then, the electrode substrate for evaluation was obtained by heat-hardening at 230 degreeC in oven for 20 minutes.

Other than that, an empty cell was manufactured by the method described in International Publication No. 2018/151079.

Liquid crystal (MLC-6608 by Merck Japan company) was inject|poured into the obtained empty cell, and the peripheral part was sealed with UV curable sealing compound. The liquid crystal cell for a measurement was completed by carrying out annealing treatment (heating at 105 degreeC in a hot-air circulation furnace, 2.5 hours) of the said liquid crystal cell.

Voltage was applied to the prepared liquid crystal cell for measurement under the conditions of a voltage of 5 V, 0.6 Hz, and a frame time of 1667 msec, and the voltage retention before ultraviolet irradiation was measured with "a liquid crystal physical property evaluation apparatus-6254 type" manufactured by Toyo Technica. Voltage retention is an indicator of electrical reliability. Moreover, it is so preferable that voltage retention is high.

And using the same apparatus, the electric current at the time of applying the triangular wave of frequency 0.1Hz and +/-3V to the liquid crystal cell for a measurement was measured over time, and the waveform of the temporal change of an electric current was obtained. The area of the impurity ion peak in the waveform was measured, and the ion density (pC) before ultraviolet irradiation was measured.

Next, the liquid crystal cell for a measurement was irradiated with the ultraviolet-ray by 18 J/cm<2> and illumination intensity of 40 mW/cm<2> with a high-pressure mercury-vapor lamp. Using the liquid crystal cell for a measurement after the ultraviolet irradiation, the voltage retention after ultraviolet irradiation and the ion density after ultraviolet irradiation were measured in the procedure similar to the above.

<NMP tolerance evaluation>

N-methylpyrrolidone (NMP) tolerance evaluation was performed in the following procedure.

First, the prepared photosensitive coloring composition was apply|coated to the IZO substrate with a spin coater so that the film thickness after heat-hardening might be set to 3.0 micrometers, and after drying under reduced pressure for 1 minute, it was dried at 90 degreeC for 140 second on a hotplate. About the obtained coating film, it exposed, without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp having an intensity of 45 mW/cm 2 at a wavelength of 365 nm was used, and the exposure amount was 50 mJ/cm 2 . 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" by Kao Corporation), shower development of 0.05 Mpa of water pressure at 25 degreeC After performing, development was stopped with pure water and washed with water washing spray. The shower development time measured the time for which an unexposed coating film was dissolved and removed beforehand, and it was set as 1.6 times of that time. Then, it heat-hardened at the oven temperature of 230 degreeC for 20 minutes, and the resist-coated board|substrate 2 was obtained. Two measurement substrates (2.5 cm x 1.0 cm) were cut out from the prepared resist coating substrate 2 and immersed in a 10 ml vial containing 8 ml of NMP. And the NMP dissolution test was implemented in the state which left still the vial bottle containing the board|substrate for a measurement for 40 minutes in an 80 degreeC thermal bath. After standing still for 40 minutes, the vial was taken out from the thermal bath, and the absorbance of the NMP eluted solution was measured with a spectrophotometer (UV-3100PC manufactured by Shimadzu Corporation) in a wavelength range of 300 to 800 nm at intervals of 1 nm. A halogen lamp and a deuterium lamp (switching wavelength 360 nm) are used for the light source, and a photomultiplier is used for the detector, and a slit width of 2 nm is the measurement condition. Moreover, the sample solution (NMP elution solution) was put into the 1 cm square quartz cell, and it measured. Absorbance is a dimensionless quantity which shows to what extent light intensity attenuates when light passes through which object in a spectroscopy method, and is defined by the following formula|equation.

A (absorbance) = -log ₁₀ (I/I ₀ ) (I: transmitted light intensity, I ₀ : incident light intensity)

In addition, when light is respectively incident on the sample solution and the NMP single solution from the same light source, the light intensity passing through the NMP single solution can be regarded as I ₀ , and the light intensity passing through the sample solution can be regarded as I . Therefore, (I/I ₀ ) of the above formula represents the light transmittance, and the absorbance A is a value obtained by logarithmic expression of the reciprocal of the transmittance. Absorbance A is a notation used when calculating the concentration and the like of a substance contained in a sample solution. In the case of absorbance A = 0, a state in which no light is absorbed (transmittance 100%) is indicated, and in the case of absorbance A = ∞, a state in which no light is transmitted (transmittance 0%) is indicated. That is, many resist coating-film components are eluted to NMP, and it has shown that NMP tolerance is bad, so that the absorbance is high. The spectral area of the measured absorbance was computed, and the following reference|standard evaluated NMP resistance. The spectral area of the absorbance as this evaluation criterion can be expressed as the sum of the absorbances at each wavelength, meaning the total of the eluted resist components.

NMP tolerance evaluation standard: Judgment by spectral area value of absorbance (wavelength 300-800 nm)

A: 100 or less

B: More than 100 and less than 200

C: over 200

<Preparation of pigment dispersion liquids 1 to 7>

The pigment, dispersant, alkali-soluble resin, and solvent shown in Table 1 were mixed so that it might become the mass ratio shown in Table 1. The dispersion treatment was performed for this liquid mixture in the range of 25-45 degreeC with a paint shaker for 3 hours. As beads, 0.5 mm phi zirconia beads were used, and 2.5 times the mass of the dispersion was added. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare pigment dispersions 1 to 7.

In addition, the quantity of the solvent derived from a dispersing agent and alkali-soluble resin is contained in the quantity of the solvent in Table 1. Moreover, the evaluation result of the viscosity of the pigment dispersion liquid measured by the method mentioned above is shown in Table 1.

[Examples 1 to 4, Comparative Examples 1 to 6]

Each component is added so that the content ratio of the solid content of each component in the total solid content becomes the value shown in Table 2, and PGMEA is added so that the content rate of the total solid content is 22 mass%, stirred and dissolved, Example 1 The photosensitive coloring compositions of -4 and Comparative Examples 1-6 were prepared. Moreover, the evaluation result of the unit OD value, voltage retention (VHR), ion density, and NMP resistance measured by the method mentioned above is shown in Table 2.

From Table 2, in the photosensitive coloring composition of Comparative Example 4, the counter ion in the repeating unit represented by the formula (1) in the dispersant-VI was not the counter anion represented by the formula (2), but a halogen ion, Voltage retention, ion density, and NMP resistance after UV irradiation all fall significantly. On the other hand, in the photosensitive coloring composition of Comparative Example 5, even if the optical density per unit film thickness was less than 0.5 and did not contain the dispersing agent described in this application, all were favorable, and the subject of this application did not generate|occur|produce. This is presumed to be because, in Comparative Example 5, there are few impurities in the pigment, free counter anions in the dispersant, and the like.

In the photosensitive coloring composition of the comparative example 1, NMP tolerance is inferior significantly. In the dispersing agent-III contained in the photosensitive coloring composition of Comparative Example 1, although the counter anion of the ammonium group forms a salt with the phosphonic acid ion derived from a weak acid, since it is derived from a weak acid, it becomes easy to return to a phosphonic acid and an amino group, NMP When it is immersed in an amine-based solvent as in .

On the other hand, in all the photosensitive coloring compositions of Comparative Examples 2 and 3, the voltage retention before ultraviolet irradiation was low, and the voltage retention after ultraviolet irradiation was still lower. This is because toluenesulfonic acid anion and benzenesulfonic acid anion, which are counter anions of ammonium groups of dispersants-IV and V contained in the photosensitive coloring compositions of Comparative Examples 2 and 3, are stable anions derived from strong acids, and thus are adsorbed to the pigment. It is presumed that the sulfonic acid anion of the surplus dispersant that has not been prepared is dissolved in the liquid crystal to lower the voltage retention, and the counter anion released by UV irradiation further increases, further lowering the voltage retention.

Moreover, in the photosensitive coloring composition of the comparative example 6, the voltage retention before ultraviolet irradiation is the low side, and the voltage retention after ultraviolet irradiation was still lower. It is presumed that methyl toluenesulfonate contained in the dispersant-VI contained in the photosensitive colorant of Comparative Example 6 is easily liberated, is further liberated by irradiation with ultraviolet light, and is dissolved in the liquid crystal to lower the voltage retention.

On the other hand, in the photosensitive coloring composition of Example 1, NMP tolerance was favorable, and both the voltage retention before ultraviolet irradiation and the voltage retention after ultraviolet irradiation were favorable.

As for this, since the counter anion represented by the said General formula (2) of the dispersing agent -I contained in the photosensitive coloring composition of Example 1 is not an anion derived from an acid, but an anion derived from an ester, an ammonium group returns to an amino group It is not thin, and it is estimated that NMP resistance is favorable.

In addition, since this counter anion is an ester-derived anion and is stably bound to an ammonium group, even when an excess dispersant remains in the cured product, it is not easily liberated as an anion in the liquid crystal, thus affecting the orientation of the liquid crystal. It is estimated that the voltage retention is good before and after UV irradiation.

Moreover, like the photosensitive coloring composition of Example 3, the voltage retention and NMP tolerance were favorable, so that unit OD was low. It is estimated that this is because there is little elution derived from the impurity of a pigment. Moreover, like the photosensitive coloring composition of Example 2 and Example 4, even if it contained the organic black pigment of Structural formula (1), voltage retention and NMP tolerance were favorable.

Claims (12)

A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photoinitiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersing agent,
An optical density of 0.5 or more per 1 μm of the film thickness of the cured coating film,
The said (f) dispersing agent contains the dispersing agent (f1) which has a repeating unit represented by following General formula (1), The photosensitive coloring composition characterized by the above-mentioned.

(In formula (1), R ¹ to R ³ are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent, and two or more of R ¹ to R ³ are bonded to each other to form a cyclic structure may be formed.
R ⁴ is a hydrogen atom or a methyl group.
X is a divalent linking group.
Y ^- is a counter anion represented by the following general formula (2).)

(In formula (2), R ⁵ is an alkyl group which may have a substituent.) The method of claim 1,
The said (a) colorant contains at least 1 type selected from the group which consists of a red pigment and an orange pigment, and at least 1 type selected from the group which consists of a blue pigment and a purple pigment, The photosensitive coloring composition. The method of claim 1,
The photosensitive coloring composition in which the said (a) colorant contains a black pigment. 4. The method of claim 3,
The photosensitive coloring composition in which the said black pigment contains an organic black pigment. The method of claim 1,
The photosensitive coloring composition whose content rate of the said (a) coloring agent is 10 mass % or more in total solid. 6. The method according to any one of claims 1 to 5,
The photosensitive coloring composition whose amine value of the said dispersing agent (f1) is 30 mgKOH/g or more. The method of claim 1,
The photosensitive coloring composition for formation of colored spacers. The hardened|cured material which hardened|cured the photosensitive coloring composition in any one of Claims 1-5 and 7. The hardened|cured material which hardened|cured the photosensitive coloring composition of Claim 6. The image display apparatus containing the hardened|cured material of Claim 8. The image display device containing the hardened|cured material of Claim 9. delete