JP7268700B2 - Photosensitive coloring composition, cured product, colored spacer, image display device - Google Patents

Description

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

A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on/off a voltage applied to the liquid crystal. On the other hand, each member constituting a cell of LCD is often formed by a method using a photosensitive composition, typified by photolithography. Since this photosensitive composition can easily form a fine structure and can be easily processed on substrates for large screens, its application range will tend to expand further in the future.

However, in LCDs manufactured using a photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electrical properties of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition. Problems such as display unevenness may occur. In particular, the effect is great for members closer to the liquid crystal layer in a color liquid crystal display, such as so-called columnar spacers and photospacers, which are used to maintain a constant gap between two substrates in a liquid crystal panel.

Conventionally, when a spacer having no light shielding property is used in a TFT type LCD, the TFT as a switching element sometimes malfunctions due to the light transmitted through the spacer. In order to prevent this, for example, Patent Document 1 describes a method of using a spacer (colored spacer) having a light shielding property.

On the other hand, in recent years, along with changes in panel structure, a method has been proposed in which colored spacers having different heights are collectively formed by photolithography. For example, in Patent Document 2, by combining a plurality of specific pigment species with different light absorption characteristics and ensuring the balance of light absorption in the ultraviolet region and the visible region, while maintaining the light shielding property and the voltage holding ratio of the liquid crystal, the shape It is disclosed that it is possible to control the height difference and the adhesion to the substrate. Further, Patent Document 3 discloses a product using a plurality of kinds of organic color pigments as a pigment, and Patent Document 4 discloses a product using an organic black pigment.

On the other hand, Patent Document 5 describes the use of a specific oxime ester compound as a highly sensitive photopolymerization initiator for the purpose of increasing curability in color filter resist applications.

Japanese Patent Laid-Open No. 8-234212 WO2013/115268 Korean Patent No. 10-1266295 Japanese special table 2014-529652 Japanese special table 2014-500852

In recent years, with the change in panel structure, there is a demand for further enhancing the light-shielding property of colored spacers. Examples of methods for increasing the light-shielding property include a method using a pigment having a high light-shielding property, and a method of increasing the content of the pigment in the photosensitive coloring composition. As a result of investigation by the present inventors, in the photosensitive coloring compositions described in Patent Documents 2 to 4, when the light-shielding property of the colored spacer is further increased by using a pigment with high light-shielding property in combination, the film surface It was found that the cross-linking density difference between the vicinity and the vicinity of the film bottom becomes large, and wrinkles occur on the coating film surface due to thermal contraction during the thermosetting process, resulting in insufficient surface smoothness.

On the other hand, Patent Document 5 describes the use of a specific oxime ester compound as a photopolymerization initiator for color resists. However, Patent Document 5 neither describes nor suggests using this oxime ester compound as a photopolymerization initiator for a photosensitive coloring composition for forming a colored spacer. Therefore, it is unknown how this oxime ester compound works when it is used as a photopolymerization initiator for a photosensitive coloring composition for forming a colored spacer.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition capable of forming a pattern having high light-shielding properties and excellent surface smoothness. do.

As a result of intensive studies by the present inventors to solve the above problems, it was found that the above problems can be solved by using a specific oxime ester compound as a photopolymerization initiator in a photosensitive coloring composition. The inventors have found the present invention.

That is, the present invention has the following configurations [1] to [14].
[1] Colored spacer formation containing (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, (d) ethylenically unsaturated compound, (e) solvent, and (f) dispersant A photosensitive coloring composition for
A photosensitive coloring composition for forming a colored spacer, wherein the (c) photopolymerization initiator contains an oxime ester compound represented by the following formula (I).

(In the above general formula (I),
R ¹ represents an aromatic ring group optionally having a substituent.
R ² represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
^R3 represents a hydrogen atom or an optionally substituted alkyl group.
^R4 represents an aromatic ring group optionally having a substituent.
R ⁵ and R ⁶ each independently represent an optionally substituted benzene ring or an optionally substituted naphthalene ring. However, at least one of R ⁵ and R ⁶ is a naphthalene ring optionally having a substituent.
At least one of R ¹ and R ⁴ has a —OR ⁷ group as a substituent. However, ^R7 represents a halogenoalkyl group.
X represents a direct bond or a carbonyl group.
Z represents a direct bond or a carbonyl group. )
[2] In [1], wherein the (a) colorant contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments. A photosensitive coloring composition for forming a colored spacer as described above.
[3] The red pigment is (1) below, the orange pigment is (2) below, the blue pigment is (3) below, and the purple pigment is (4) below. , the photosensitive coloring composition for forming a colored spacer according to [2].
(1) C.I. I. Pigment Red 177, at least one selected from 254 (2) C.I. I. Pigment Orange 43, at least one selected from 64 (3) C.I. I. Pigment Blue 15: at least one selected from 6 and 60 (4) C.I. I. Pigment Violet 23, 29 [4] The content of at least one pigment selected from the group consisting of red pigments and orange pigments is 1 part by mass with respect to 100 parts by mass of the colorant (a) The photosensitive coloring composition for forming a colored spacer according to [2] or [3], which is 30 parts by mass or less.
[5] The content ratio of at least one pigment selected from the group consisting of a blue pigment and a purple pigment is 20 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the coloring agent (a). The photosensitive coloring composition for forming a colored spacer according to any one of [4].
[6] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [5], wherein (a) the coloring agent contains an organic black pigment.
[7] The photosensitive material for forming a colored spacer according to [6], wherein the organic black pigment contains a compound represented by the following formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof. sexually colored composition.

(In formula (1) above, R ¹¹ and R ¹⁶ are each independently 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 independently of each other hydrogen atoms, halogen atoms, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , ^{CONHR21 , CONR21R22 ,} CN, ^OH , ^OR21 , ^COCR21 , _OOCNH2 , ^OOCNHR21 , ^OOCNR21R22 , _NO2 , _NH2 , ^NHR21 , ^NR21R22 , ^NHCOR22 , ^{NR21 COR22} , N= _CH2 , N= ^CHR21 , N= ^CR21R22 , SH, ^SR21 _, ^{SOR21 ,} _SO2R21 ^{, SO3R21} , _SO3H ^, _{SO3- , SO2NH2} , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;
and at least one combination selected from the group consisting of ^R12 and ^R13 , ^R13 and ^R14 , ^R14 and ^R15 , ^R17 and ^R18 , ^R18 and ^R19 , and ^R19 and ^R20 , directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, an NH or an 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 a carbon It is an alkynyl group of numbers 2 to 12. )
[8] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [7], wherein the coloring agent (a) contains carbon black.
[9] The photosensitive coloring composition for forming a colored spacer according to [1], wherein (a) the coloring agent contains an organic pigment and carbon black.
[10] The photosensitive coloring composition for forming a colored spacer according to [9], wherein the organic pigment contains at least one selected from the group consisting of red pigments, orange pigments, blue pigments and violet pigments.
[11] The photosensitive coloring composition for forming a colored spacer according to [9] or [10], wherein the organic pigment contains at least one selected from the group consisting of the following (1) to (4).
(1) C.I. I. Pigment Red 177, at least one selected from 254 (2) C.I. I. Pigment Orange 43, at least one selected from 64 (3) C.I. I. Pigment Blue 15: at least one selected from 6 and 60 (4) C.I. I. Pigment Violet 23, 29 [12] The photosensitive coloring composition for forming a colored spacer according to any one of [9] to [11], wherein the organic pigment contains a blue pigment and a violet pigment. thing.
[13] The photosensitive material for forming a colored spacer according to any one of [9] to [12], wherein the content of carbon black with respect to 100 parts by mass of the coloring agent (a) is 5 parts by mass or more and 50 parts by mass or less. coloring composition.
[14] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [13], wherein the cured coating film has an optical density of 1.0 or more per 1 μm of film thickness.
[15] The photosensitive coloring composition for forming colored spacers according to any one of [1] to [14], which is used for collectively forming colored spacers having different heights by photolithography.
[16] A cured product obtained by curing the photosensitive coloring composition for forming a colored spacer according to any one of [1] to [15].
[17] A colored spacer formed from the cured product of [16].
[18] An image display device comprising the colored spacer of [17].

ADVANTAGE OF THE INVENTION According to this invention, the light-shielding property is high and the photosensitive coloring composition which can form the pattern excellent in surface smoothness can be provided. In addition, it is possible to provide a cured product and a colored spacer that are excellent in light-shielding properties and surface smoothness, and furthermore, it is possible to provide an image display device comprising such a colored spacer.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

"(Co)polymer" means including both a single polymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydride) ... acid" , is meant to include both acids and their anhydrides. In the present invention, the "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing a (meth)acrylic acid ester having a carboxyl group.

In the present invention, the term "monomer" is a term corresponding to so-called high-molecular substances (polymers), and in addition to narrowly defined monomers (monomers), it also includes dimers, trimers, oligomers, and the like. is.

In the present invention, the "total solid content" means all components other than the solvent contained in the photosensitive coloring composition or the ink described later.

In the present invention, the "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).

In the present invention, unless otherwise specified, the "amine value" represents the amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. is. In addition, the measuring method will be described later. On the other hand, the "acid value" means the acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

Moreover, in this specification, percentages and parts represented by "mass" are synonymous with percentages and parts represented by "weight".

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(a) a coloring agent (b) an alkali-soluble resin (c) a photopolymerization initiator (d) an ethylenically unsaturated compound (e) a solvent (f) a dispersant are contained as essential components. Further, the photosensitive coloring composition of the present invention, if necessary, further includes an adhesion improver such as a silane coupling agent, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment. It contains other compounding components such as derivatives, and each compounding component is usually used in a state of being dissolved or dispersed in a solvent.

The photosensitive coloring composition of the present invention has a high light-shielding property and can form a pattern with excellent surface smoothness, so it can be preferably used for forming a colored spacer, that is, a photosensitive for forming a colored spacer It can be suitably used as a coloring composition.

On the other hand, properties such as light-shielding properties and surface smoothness are also required for applications other than colored spacers, such as, for example, the partition walls of the light-emitting portion of an organic EL display device, particularly colored partition walls (colored banks). It can be used without being limited to spacers. The photosensitive coloring composition of the present invention will be described in detail below, and unless otherwise specified, both the use as a colored spacer and the use other than as a colored spacer will be described together.

In the photosensitive coloring composition according to the first aspect of the present invention, (a) the coloring agent is at least one selected from the group consisting of red pigments and orange pigments, and selected from the group consisting of blue pigments and violet pigments. and (c) the photopolymerization initiator contains an oxime ester compound represented by formula (I) described below.

Further, the photosensitive coloring composition according to the second aspect of the present invention includes (a) a compound in which the coloring agent is represented by the general formula (1) described later, a geometric isomer thereof, a salt thereof, or a geometric isomer thereof (hereinafter sometimes abbreviated as "the organic black pigment represented by the general formula (1)") which is a salt of.

Further, in the photosensitive coloring composition according to the third aspect of the present invention, (a) the coloring agent contains an organic pigment and carbon black, and (c) the photopolymerization initiator contains the following formula (I ) contains an oxime ester compound represented by

On the other hand, the photosensitive coloring composition according to the fourth aspect of the present invention is a photosensitive coloring composition for forming a colored spacer, and (c) the photopolymerization initiator is represented by the below-described formula (I) including oxime ester compounds.

Hereinafter, unless otherwise specified, the "photosensitive coloring composition of the present invention" refers to all of the photosensitive coloring compositions according to the first to fourth aspects.

<(a) Colorant>
The (a) colorant used in the photosensitive coloring composition according to the first aspect of the present invention is at least one selected from the group consisting of red pigments and orange pigments, and selected from the group consisting of blue pigments and violet pigments. contains at least one. As described above, the photosensitive coloring composition according to the first aspect of the present invention can achieve high light-shielding properties by containing a specific organic coloring pigment.

(a) It is preferable to use a pigment as the colorant. As the pigment, an inorganic pigment or an organic pigment may be used. It is preferable to use an organic pigment from the viewpoint of suppressing a decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to make it easier to control the shape and steps.

The chemical structure of these pigments is not particularly limited. For example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based organic pigments as well as various inorganic pigments can be used. Specific examples of pigments that can be used are shown below by pigment numbers. In the following, terms such as "C.I. Pigment Red 2" refer to the Color Index (C.I.).

As a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.

Among these, C.I. I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.

In terms of dispersibility and light-shielding properties, C.I. I. Pigment Red 177, 254, 272 is preferably used. When the photosensitive coloring composition according to the first aspect of the present invention is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. From this point of view, C.I. I. Pigment Red 254, 272 is more preferably used.

As an orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.

Among these, C.I. I. Pigment Orange 38, 71 may be mentioned. In terms of dispersibility and light-shielding properties, C.I. I. Pigment Orange 43, 64, 72 is preferably used. When the photosensitive coloring composition according to the first aspect of the present invention is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. From this point of view, C.I. I. More preferably, Pigment Orange 64, 72 is used.

As a blue pigment, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned.

Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.

In terms of dispersibility and light-shielding properties, C.I. I. Pigment Blue 15:6,16,60 is preferably used. When the photosensitive coloring composition according to the first aspect of the present invention is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. From this point of view, C.I. I. Pigment Blue 60 is more preferably used.

As a purple pigment, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.

Among these, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.

In terms of dispersibility and light-shielding properties, C.I. I. Pigment Violet 23, 29 is preferably used. When the photosensitive coloring composition according to the first aspect of the present invention is cured with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate. From this point of view, C.I. I. Pigment Violet 29 is more preferably used.

Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and violet pigments include green pigments and yellow pigments.

As a green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned. Among these, C.I. I. Pigment Green 7, 36 can be mentioned.

As a yellow pigment, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 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 can be mentioned.

Among these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

Among these, from the viewpoint of light-shielding properties and control of shape and steps, it is preferable to contain at least one of the following pigments.
Red pigment: C.I. I. Pigment Red 177, 254, 272
Orange pigment: C.I. I. Pigment Orange 43, 64, 72
Blue pigment: C.I. I. pigment blue 15:6,60
Purple pigment: C.I. I. Pigment Violet 23, 29

In addition, from the viewpoint of light-shielding properties and control of shape and steps, the red pigment is preferably the following (1), the orange pigment is preferably the following (2), and the blue pigment is the following ( 3) is preferable, and the purple pigment is preferably the following (4).
(1) C.I. I. Pigment Red 177, at least one selected from 254 (2) C.I. I. Pigment Orange 43, at least one selected from 64 (3) C.I. I. Pigment Blue 15: at least one selected from 6 and 60 (4) C.I. I. At least one selected from Pigment Violet 23 and 29

Although the combination of colors is not particularly limited, from the viewpoint of light blocking properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment and a violet pigment, and the like. .

Furthermore, in addition to these coloring pigments, a black colorant can be used.
Among black colorants, it is preferable to use an organic black pigment from the viewpoint of suppressing a decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to facilitate control of the shape and steps, particularly light shielding. From the viewpoint of compatibility, it is preferable to use an organic black pigment which is a compound represented by the following formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof.

In formula (1), R ¹¹ and R ¹⁶ are each independently 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 independently of each other hydrogen atoms, halogen atoms, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , ^{CONHR21 , CONR21R22 ,} CN, ^OH , ^OR21 , ^COCR21 , _OOCNH2 , ^OOCNHR21 , ^OOCNR21R22 , _NO2 , _NH2 , ^NHR21 , ^NR21R22 , ^NHCOR22 , ^{NR21 COR22} , N= _CH2 , N= ^CHR21 , N= ^CR21R22 , SH, ^SR21 _, ^{SOR21 ,} _SO2R21 ^{, SO3R21} , _SO3H ^, _{SO3- , SO2NH2} , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;
and at least one combination selected from the group consisting of ^R12 and ^R13 , ^R13 and ^R14 , ^R14 and ^R15 , ^R17 and ^R18 , ^R18 and ^R19 , and ^R19 and ^R20 , directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, an NH or an 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 a carbon It is an alkynyl group of numbers 2 to 12.

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

When the compound of general formula (1) is anionic, its charge can be transferred to any known suitable cation, such as metallic, organic, inorganic or metal-organic cations, especially alkali metals, alkaline earth metals. , transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium or salts compensated by organometallic complexes. Moreover, when the geometric isomer of the compound represented by general formula (1) is anionic, it is preferably a similar salt.

In the substituents of the general formula (1) and their definitions, the following are preferable because the shielding rate tends to be high. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.

R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R ¹³ and R ¹⁸ independently of each other are preferably hydrogen, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine, chlorine, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ ) (C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^— , more preferably a hydrogen atom or SO ₃ H;

R ¹¹ and R ¹⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , 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 is the same as R ¹⁶ , R ¹² is the same as R ¹⁷ , R ¹³ is the same as R ¹⁸ , R ¹⁴ is the same as R ¹⁹ , and R ^{15 is} the same as R ²⁰ are identical.

Alkyl groups having 1 to 12 carbon atoms are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n -pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2- ethylhexyl, nonyl, decyl, undecyl or dodecyl.

Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thuzyl, norbornyl, bornyl, and norcalyl groups. , a karyl group, a menthyl group, a norpinyl group, a pinyl group, a 1-adamantyl group or a 2-adamantyl group.

Alkenyl groups having 2 to 12 carbon atoms are, for example, vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1,3-butadiene -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2-buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group or dodecenyl group.

Cycloalkenyl groups having 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2 , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group or camphenyl group.

Alkynyl groups having 2 to 12 carbon atoms are, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 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-octin-8-yl group, 1-nonin-9-yl group, 1-decyn-10-yl group or 1-dodecyn-12-yl group.

A 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).

A specific example of such an organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
This organic black pigment is preferably used by dispersing it with a dispersant, solvent, and method, which will be described later. Further, when the sulfonic acid derivative of the general formula (2) is present during dispersion, the dispersibility and storage stability may be improved.

Black colorants other than the organic black pigment represented by the general formula (1) include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and the like. is mentioned. Among these, carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics. Examples of carbon black include the following carbon blacks.

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

Degussa: Printex (registered trademark, hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex x L, Printex G, Printex P, Printex U, Printex V, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW 1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Cabot Corporation: Monarch (registered trademark, the same applies hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same applies hereinafter) 99, RE GAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark)-8

Made by Columbian Carbon: RAVEN (registered trademark, hereinafter the same) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RA VEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black that is coated with a resin may be used. The use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate and the volume resistivity. As the resin-coated carbon black, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

The total content of Na and Ca is preferably 100 ppm or less as the carbon black to be coated with the resin. Carbon black usually contains Na, Ca, K, Mg, Al, Fe mixed from raw material oil and combustion oil (or gas) at the time of production, reaction stop water and granulation water, and furnace materials of reactors. etc., and contains ash in the order of percent. Of these, Na and Ca are generally contained in amounts of several hundred ppm or more, respectively. tend to prevent short circuits.

As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw material oil, fuel oil (or gas) and reaction stop water when producing carbon black. and by minimizing the amount of the alkaline substance added to adjust the structure. Another method is to wash the carbon black produced from the furnace with water or hydrochloric acid to dissolve and remove Na and Ca.

Specifically, carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide solution, and then a solvent that is sparingly soluble in water is added. Carbon black migrates to the solvent side and is completely separated from water. Most of Na and Ca present in the carbon black together with the carbon black are dissolved and removed in water and acid. 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 with carefully selected raw materials or the water or acid dissolution method alone. The total amount of Na and Ca can be easily made 100 ppm or less.

Also, the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it is possible to coat even fine units, which is preferable. Furthermore, 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. Within the above range, there is a tendency to obtain a coating film having good light-shielding properties. The average particle diameter means the number average particle diameter. Particle image analysis is performed by taking photographs taken at tens of thousands of times by electron microscope observation and measuring about 2000 to 3000 particles in these photographs with an image processing device. means the equivalent circle diameter determined by

The method of preparing the resin-coated carbon black is not particularly limited. A resin solution obtained by mixing a resin with a solvent such as cyclohexanone, toluene, or xylene and dissolving it by heating, and a suspension obtained by mixing carbon black and water are mixed and stirred to separate carbon black and water, and then 2. A method of forming a composition obtained by removing water and heating and kneading into a sheet, pulverizing, and then drying; A method of mixing and stirring the resin solution and suspension prepared in the same manner as described above to granulate the carbon black and resin, and then separating and heating the resulting granules to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and a resin is added thereto. 4. dry blending with a hand; A reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, which is cooled after polymerization to obtain a reactive group-containing resin from the polymer suspension. A method of adding carbon black, kneading, reacting the carbon black with a reactive group (grafting the carbon black), cooling, and pulverizing can be adopted.

The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins with benzene rings in the structure have a stronger action like amphoteric surfactants, so they can be dispersed. It is preferable from the point of view of properties and dispersion stability.

Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenyleneterephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone can be used.

The coating amount of the resin with respect to the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin. On the other hand, when the content is equal to or less than the above upper limit, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.

Carbon black coated with a resin in this way can be used as a light-shielding material for colored spacers in a conventional manner, and a color filter comprising the colored spacer as a component can be produced in a conventional manner. 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. It is also presumed that the coating of the carbon black surface with a resin also works to enclose Ca and Na in the carbon black.

In addition to the above organic coloring pigments and black coloring materials, dyes may also be used. Dyes that can be used as coloring materials include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. mordant black 7 and the like.

Examples of anthraquinone dyes include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like can be mentioned.
In addition, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like are quinone imine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro-based dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include Disperse Yellow 42 and the like.

These pigments are preferably dispersed so that the average particle size is generally 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the standard for the average particle size is the number of pigment particles.

In addition, in the photosensitive coloring composition according to the first aspect of the present invention, the average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is performed with a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, that concentration) and measured at 25°C.

On the other hand, the (a) colorant used in the photosensitive coloring composition according to the second aspect of the present invention is a compound represented by the general formula (1), a geometric isomer thereof, a salt thereof, or a geometric isomer thereof Contains organic black pigments that are salts of the body. Thus, it is considered that a low dielectric constant and a high light shielding rate can be realized by including a specific organic black pigment.

The (a) coloring agent used in the second aspect of the present invention may contain other coloring agents in addition to the organic black pigment. As another coloring agent, it is preferable to use a pigment. The pigment may be an organic pigment or an inorganic pigment. From the viewpoint of facilitating control of the shape and steps, it is more preferable to use an organic pigment. As the organic pigment, those mentioned in the first aspect can be used.

Furthermore, in addition to these pigments, other black colorants can be used.
Among other black color materials, from the viewpoint of suppressing a decrease in the voltage holding ratio of liquid crystals and suppressing the absorption of ultraviolet rays to facilitate control of the shape and steps, it is represented by the general formula (1). It is preferable to use other organic black pigments other than the above. Other organic black pigments include aniline black, perylene black, cyanine black and the like.

Moreover, an inorganic black pigment can be used in the second aspect of the present invention. Examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like. Among these, carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics. As examples of carbon black, those mentioned in the first aspect can be used. Further, other coloring materials such as the dyes mentioned in the first aspect can also be used.

The (a) colorant used in the photosensitive coloring composition according to the third aspect of the present invention contains an organic pigment and carbon black. Thus, by using an organic pigment that absorbs little ultraviolet light, it is easy to control the shape and steps, and by using carbon black in addition to the organic pigment, it is possible to achieve high light-shielding properties.

Although the type of organic pigment is not particularly limited, it preferably contains at least one selected from the group consisting of red pigments, orange pigments, blue pigments and violet pigments from the viewpoint of adhesion. As the red pigment, orange pigment, blue pigment and violet pigment, those mentioned in the first aspect can be used.

Among these, from the viewpoint of light-shielding properties and control of shape and level difference, it is preferable to contain at least one of the following (1) to (4).
(1) C.I. I. Pigment Red 177, at least one selected from 254 (2) C.I. I. Pigment Orange 43, at least one selected from 64 (3) C.I. I. Pigment Blue 15: at least one selected from 6 and 60 (4) C.I. I. At least one selected from Pigment Violet 23 and 29

Among these, it is preferable to use a blue pigment and/or a violet pigment from the viewpoint of light shielding properties in the visible region, particularly in the long wavelength region. In particular, the absorption spectrum of carbon black has a downward slope from short to long wavelengths, and the absorbance in the ultraviolet region is higher than that of organic pigments. From the viewpoint of , it is preferable to use a blue pigment and/or a violet pigment and carbon black together, and it is more preferable to use a blue pigment and/or a violet pigment and carbon black together.

Moreover, from the viewpoint of light-shielding properties, the organic pigment preferably contains an organic black pigment. As the organic black pigment, those mentioned in the first aspect can be used. In addition, other organic coloring pigments listed in the first aspect, other black colorants, dyes, and the like can also be used.

The (a) coloring agent used in the photosensitive coloring composition for forming a colored spacer according to the fourth aspect of the present invention is not particularly limited as long as it can form a desired colored spacer. For example, from the viewpoint of suppressing the absorption of ultraviolet rays and making it easier to control the shape and steps, at least one selected from the group consisting of red pigments and orange pigments described above as the first embodiment, and blue pigments and purple pigments. It preferably contains at least one selected from the group consisting of pigments.

Thus, the (a) coloring agent used in the photosensitive coloring composition for forming a colored spacer according to the fourth aspect is described as the (a) coloring agent used in the photosensitive coloring composition according to the first aspect. can be applied, and those described as the (a) colorant used in the photosensitive coloring composition according to the second or third aspect can also be applied.

On the other hand, the photosensitive coloring composition for forming a colored spacer according to the fourth aspect preferably contains at least a black colorant, and at least carbon black, from the viewpoint of light-shielding properties. is more preferred. In addition, it is more preferable to contain at least the organic black pigment from the viewpoint of suppressing a decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to make it easier to control the shape and steps. Carbon black and an organic black pigment may be used in combination from the viewpoint of light shielding properties, suppression of a decrease in voltage holding ratio of liquid crystal, and controllability of shapes and steps.

In the photosensitive coloring composition for forming a colored spacer according to the fourth aspect, the preferred values for the photosensitive coloring composition of the present invention described later can be adopted as the blending amount of these coloring agents. In addition, it can be adjusted as appropriate according to the required optical density, International Publication No. 2013/062011, International Publication No. 2013/115268, Japanese Special Table 2014-534460, Japanese Special Table 2014-529652 JP-A-2014-146029, International Publication No. 2013/179237, JP-A-2011-107707, etc. can also be employed.

<(b) Alkali-soluble resin>
The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group. Urethane resins, novolak-based resins, polyvinylphenol-based resins, and the like can be mentioned, and among them, epoxy (meth)acrylate-based resins and acrylic-based resins are preferable. These can be used individually by 1 type or in mixture of multiple types.

The (b) alkali-soluble resin used in the present invention is particularly the following alkali-soluble resin (b1) and/or alkali-soluble resin (b2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin"). is preferably used from the viewpoint of excellent plate-making properties.

<Alkali-soluble resin (b1)>
Obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or its anhydride. Alkali-soluble resin.
<Alkali-soluble resin (b2)>
An α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and/or its anhydride. Alkali-soluble resin obtained by

Examples of epoxy resins used as raw materials include bisphenol A type epoxy resins (e.g., "Epikote (registered trademark; hereinafter the same) 828", "Epikote 1001", "Epikote 1002", "Epikote 1004", etc. manufactured by Mitsubishi Chemical Corporation). ), epoxy obtained by the reaction of the alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.)), bisphenol F type resin ( For example, "Epikote 807", "EP-4001", "EP-4002", "EP-4004, etc." manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin. (For example, Nippon Kayaku "NER-7406" (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, Mitsubishi Chemical "YX-4000"), Phenolic novolak type epoxy resin (e.g., Nippon Kayaku Co., Ltd. "EPPN-201", Mitsubishi Chemical Co., Ltd. "EP-152", "EP-154", Dow Chemical Co., Ltd. "DEN-438"), ( o, m, p-) cresol novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd. "EOCN (registered trademark; hereinafter the same)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl Isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resin (e.g., "EPPN (registered trademark) -501", "EPN" manufactured by Nippon Kayaku Co., Ltd.) -502", "EPPN-503"), alicyclic epoxy resins ("Celoxide 2021P" and "Celoxide (registered trademark; hereinafter the same) EHPE" manufactured by Daicel Chemical Industries, Ltd.), by the reaction of dicyclopentadiene and phenol Epoxy resins obtained by glycidylating phenolic resins (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (B1) to (B4) , etc. can be suitably used.

Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B2) NC-3000", and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4).

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

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

In general formula (B3) above, X represents a linking group represented by general formula (B3-1) or (B3-2) below. However, it contains one or more adamantane structures in its molecular structure. c represents an integer of 2 or 3;

In general formulas (B3-1) and (B3-2) above, R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ are each independently an optionally substituted adamantyl group, a hydrogen atom, or a substituent. or an optionally substituted phenyl group. * indicates a bond.

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

Among these, epoxy resins represented by any one of general formulas (B1) to (B4) are preferably used.

Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth) ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl adipic acid, 2-( meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2-( meth) acryloyloxypropyl adipate, 2-(meth) acryloyloxypropyl tetrahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) acryloyloxypropyl maleate, 2-(meth) ) acryloyloxybutyl succinate, 2-(meth) acryloyloxybutyl adipate, 2-(meth) acryloyloxybutyl hydrophthalate, 2-(meth) acryloyloxybutyl phthalate, 2-(meth) Acryloyloxybutyl maleate (meth), a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to acrylic acid, or hydroxyalkyl ( Monomers obtained by adding acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to pentaerythritol tri(meth)acrylate, and (meth)acrylic acid dimers etc.
Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method for adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known technique can be used. For example, it is possible to react an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. can.

Examples of the esterification catalyst used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride. .

The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly or in combination of two. The above may be used in combination.

The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. , more preferably in the range of 0.7 to 1.1 equivalents.

If the amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of the unsaturated group introduced is insufficient, resulting in subsequent polybasic acid and/or its anhydride. The reaction with is also insufficient. It is also not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, a tendency of deterioration in curing properties is recognized.

Polybasic acids and/or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid. One or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrides thereof, and the like.

Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof are preferred. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, and biphenyltetracarboxylic dianhydride.

A known method can also be used for the addition reaction of polybasic acids and/or their anhydrides, and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid having a carboxyl group to an epoxy resin. The desired product can be obtained by continuing the reaction under the same conditions as the ester addition reaction.

The added amount of the polybasic acid and/or its anhydride component is such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and still more preferably 50 mgKOH/g. g or more. Also, it is preferably in the range of 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, still more preferably 120 mgKOH/g. Alkali developability tends to be improved by setting the amount to the above lower limit or more, and curing performance tends to be improved by setting the amount to the above upper limit or less.

A multi-branched structure may be introduced by adding a polyfunctional alcohol such as trimethylolpropane, pentaerythritol, or dipentaerythritol during the addition reaction of the polybasic acid and/or its anhydride.

A carboxyl group-containing epoxy (meth)acrylate resin is usually prepared by adding a polybasic acid and / Or after mixing the anhydride, or in the reaction product of the epoxy resin and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, a polybasic acid and / Alternatively, it can be obtained by heating after mixing the anhydride and polyfunctional alcohol.

In this case, the order of mixing the polybasic acid and/or its anhydride and the polyfunctional alcohol is not particularly limited. By heating, any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol A polybasic acid and/or its anhydride undergoes an addition reaction.

The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, and further It is preferably 3000 or more, particularly preferably 4000 or more. Also, it is usually 10,000 or less, preferably 8,000 or less, more preferably 6,000 or less. If the weight average molecular weight is small, the solubility in the developer is high, and if it is too large, the solubility in the developer is low.

A carboxyl group-containing epoxy (meth)acrylate resin may be used alone, or two or more resins may be mixed and used.

Also, a part of the carboxyl group-containing epoxy (meth)acrylate resin described above may be replaced with another binder resin. That is, a carboxyl group-containing epoxy (meth)acrylate resin and another binder resin may be used in combination. In this case, the ratio of the carboxyl group-containing epoxy (meth)acrylate resin in the (b) alkali-soluble resin is preferably 50% by mass or more, particularly 80% by mass or more.

Other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth)acrylate resin are not limited, and may be selected from resins commonly used in photosensitive coloring compositions. Examples thereof include binder resins described in JP-A-2007-271727, JP-A-2007-316620, JP-A-2007-334290, and the like. Any of the other binder resins may be used alone or in combination of two or more.

In addition, as the alkali-soluble resin (b), from the viewpoint of compatibility with pigments, dispersants, etc., it is preferable to use acrylic resins, and those described in Japanese Patent Application Laid-Open No. 2014-137466 can be preferably used. can.

Examples of acrylic resins include ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "unsaturated monomers (b1)") and other copolymerizable ethylenically unsaturated monomers. A copolymer with a monomer (hereinafter referred to as "unsaturated monomer (b2)") can be mentioned.

Examples of unsaturated monomers (b1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacon Acids, unsaturated dicarboxylic acids such as itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or their anhydrides; succinic acid mono [2-(meth)acryloyloxyethyl], phthalic acid mono [2-(meth) Mono[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids with a valence of 2 or more, such as acryloyloxyethyl]; polymer mono(meth)acrylate; p-vinylbenzoic acid, and the like.
These unsaturated monomers (b1) can be used alone or in combination of two or more.

Examples of the unsaturated monomer (b2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α- aromatic vinyl compounds such as methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 ~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2-10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) ) 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 paracumylphenol (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (meth)acrylic acid esters such as meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane macromonomers having a mono(meth)acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate and polysiloxane;
These unsaturated monomers (b2) can be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. , more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, there is a tendency that a photosensitive colored composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, Japan Japanese Unexamined Patent Publication No. 10-31308, Japanese Unexamined Patent Publication No. 10-300922, Japanese Unexamined Patent Publication No. 11-174224, Japanese Unexamined Patent Publication No. 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japan Copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728 and the like can be mentioned.

A copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) can be produced by a known method. The structure, Mw, and Mw/Mn can also be controlled by the methods disclosed in Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 2007/029871, and the like.

<(c) Photoinitiator>
(c) The photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. Additives such as polymerization accelerators (chain transfer agents) and sensitizing dyes may be added as necessary.

The (c) photopolymerization initiator in the photosensitive coloring composition of the present invention contains an oxime ester compound represented by the following formula (I). Thus, by containing the oxime ester compound represented by the following formula (I), the naphthalene ring contained in the carbazole skeleton increases the absorbance for long-wavelength light and increases the crosslink density inside the coating film. In addition, since it has a halogen atom in its structure, the compound is easily distributed on the coating film surface, and it is thought that it is possible to suppress an excessive increase in the crosslink density on the film surface due to the influence of oxygen inhibition. be done.

In the above general formula (I),
R ¹ represents an aromatic ring group optionally having a substituent.
R ² represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
^R3 represents a hydrogen atom or an optionally substituted alkyl group.
^R4 represents an aromatic ring group optionally having a substituent.
R ⁵ and R ⁶ each independently represent an optionally substituted benzene ring or an optionally substituted naphthalene ring. However, at least one of R ⁵ and R ⁶ is a naphthalene ring optionally having a substituent.
At least one of R ¹ and R ⁴ has a —OR ⁷ group as a substituent. However, ^R7 represents a halogenoalkyl group.
X represents a direct bond or a carbonyl group.
Z represents a direct bond or a carbonyl group.

The aromatic ring group for R ¹ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The carbon number is preferably 30 or less, more preferably 12 or less, even more preferably 8 or less. Moreover, it is usually 4 or more, preferably 6 or more. When it is equal to or less than the upper limit, the solubility tends to be good, and when it is equal to or more than the lower limit, it tends to be easy to achieve both sensitivity and solubility.

An aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring of the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

A heteroaromatic ring group also means a heteroaromatic ring having one free atomization. The aromatic heterocyclic ring of the aromatic heterocyclic group may be a single ring or a condensed ring, such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring and imidazole ring. , oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene rings and the like.

Examples of substituents that the aromatic ring group may have include alkyl groups, hydroxyl groups, alkoxy groups, halogen atoms, halogenoalkyl groups (alkyl groups in which some or all of the hydrogen atoms are substituted with halogen atoms), halogeno Examples thereof include alkoxy groups (alkoxy groups in which some or all of the hydrogen atoms are substituted with halogen atoms), and halogen atoms, halogenoalkyl groups, or halogenoalkoxy groups are preferred from the viewpoint of surface curability, and are easy to synthesize. From the viewpoint of, it is preferably unsubstituted.

Among these, from the viewpoint of sensitivity, an optionally substituted aromatic hydrocarbon ring group is preferred, and an optionally substituted benzene ring group is more preferred.

Although the number of carbon atoms in the alkanoyl group in R ² is not particularly limited, it is preferably 2 or more from the viewpoint of sensitivity. From the viewpoint of sensitivity, it is preferably 20 or less, more preferably 12 or less, even more preferably 7 or less, even more preferably 5 or less, and particularly preferably 3 or less. .

Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group. Among these, from the viewpoint of sensitivity, an acetyl group or a propanoyl group is preferred, and an acetyl group is more preferred.
Examples of substituents that the alkanoyl group may have include a hydroxyl group, an alkoxy group, and a halogen atom, and are preferably unsubstituted from the viewpoint of sensitivity.

Although the number of carbon atoms in the aryloyl group in R ² is not particularly limited, it is preferably 7 or more from the viewpoint of sensitivity. From the viewpoint of sensitivity, it is preferably 20 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less.

Specific examples of the aryloyl group include a benzoyl group, a methylbenzoyl group, a naphthoyl group, etc. Among these, a benzoyl group is more preferable from the viewpoint of sensitivity.

Substituents which the aryloyl group may have include a hydroxyl group, an alkoxy group, a halogen atom and the like, and are preferably unsubstituted from the viewpoint of sensitivity.
Among these, from the viewpoint of sensitivity, R ² is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and still more preferably an acetyl group.

The number of carbon atoms in the alkyl group in R ³ is not particularly limited, but from the viewpoint of solubility, it is preferably 1 or more, more preferably 2 or more, further preferably 5 or more, and 7 or more. is particularly preferred. From the viewpoint of compatibility, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group. An octyl group or a 2-ethylhexyl group is preferred, and a 2-ethylhexyl group is more preferred.

Examples of the substituent that the alkyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, a phosphoric acid group, and the like, and from the viewpoint of ease of synthesis, it is more preferably unsubstituted.
Among these, from the viewpoint of solubility, R ³ is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and a 2-ethylhexyl group. More preferred.

The aromatic ring group for R ⁴ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The carbon number is preferably 30 or less, more preferably 12 or less, even more preferably 8 or less. Moreover, it is usually 4 or more, preferably 6 or more. When it is equal to or less than the upper limit, the solubility tends to be good, and when it is equal to or more than the lower limit, it tends to be easy to achieve both sensitivity and solubility.

An aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring of the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

A heteroaromatic ring group also means a heteroaromatic ring having one free atomization. The aromatic heterocyclic ring of the aromatic heterocyclic group may be monocyclic or condensed. For example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring , quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.

Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, and a halogen atom. From the viewpoint of solubility, an alkyl group or an alkoxy group is preferable, and an alkyl group is more preferable. , methyl groups are more preferred.

Although the number of substituents is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more from the viewpoint of solubility. From the viewpoint of compatibility, it is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.

Among these, from the viewpoint of solubility, R ⁴ is preferably an aromatic hydrocarbon ring group which may have a substituent, and an aromatic hydrocarbon ring group having two or more methyl groups. is more preferred, and a mesityl group is even more preferred.

R ⁵ and R ⁶ each independently represent an optionally substituted benzene ring or naphthalene ring. However, at least one of R ⁵ and R ⁶ is a naphthalene ring optionally having a substituent. Specific combinations include a combination in which R ⁵ is an optionally substituted benzene ring, R ⁶ is an optionally substituted naphthalene ring, and R ⁵ has a substituent an optionally substituted naphthalene ring, R ⁶ is an optionally substituted benzene ring, R ⁵ is an optionally substituted naphthalene ring, and R ⁶ is an optionally substituted benzene ring; An optional naphthalene ring combination is included.

Among these, from the viewpoint of light absorption, a combination in which R ⁵ is an optionally substituted naphthalene ring and R ⁶ is an optionally substituted benzene ring is exemplified. .

In the case where ^R5 is a benzene ring which may have a substituent, examples include a mode in which an N atom is bonded to the 1-position of the benzene ring, ^R6 is bonded to the 2-position, and X is bonded to the 4-position. Similarly, when R ⁶ is a benzene ring which may have a substituent, there is an embodiment in which an N atom is bonded to the 1-position of the benzene ring, R ⁵ is bonded to the 2-position, and Z is bonded to the 4-position. mentioned.

On the other hand, when R ⁵ is an optionally substituted naphthalene ring, the X, N atom and R ⁶ bonded to R ⁵ in formula (I) are good. For example, an N atom is bonded to the 1-position of the naphthalene ^ring , R ⁶ is bonded to the 2-position, and X is bonded to the 4-position. is bonded and X is bonded to the 6-position.

Similarly, when R ⁶ is an optionally substituted naphthalene ring, the Z, N atom, and R ⁵ bonded to R ⁶ in formula (I) are bonded to the naphthalene ring at what position. good too. For example, an N atom is ^bonded to the 1-position of the naphthalene ring, R ⁵ is bonded to the 2-position, and Z is bonded to the 4-position; is bonded and Z is bonded to the 6-position.

Examples of substituents that the benzene ring and naphthalene ring in R ⁵ and R ⁶ may have include a hydroxyl group, an alkoxy group, and a halogen atom, and unsubstituted is more preferable from the viewpoint of sensitivity.

At least one of R ¹ and R ⁴ has a —OR ⁷ group as a substituent. R ¹ may have a —OR ⁷ group, R ⁴ may have a —OR ⁷ group, and R ¹ and R ⁴ may each independently have a —OR ⁷ group . Among these, from the viewpoint of sensitivity, it is preferable that R ¹ has an —OR ⁷ group.

Although R ⁷ represents a halogenoalkyl group, the number of carbon atoms in the halogenoalkyl group in R ⁷ is not particularly limited, but from the viewpoint of solubility, it is preferably 1 or more, more preferably 2 or more, and 3 or more. It is even more preferable to have From the viewpoint of compatibility, it is preferably 10 or less, more preferably 7 or less, and even more preferably 5 or less.
The carbon chain in the halogenoalkyl group may be linear, branched, or cyclic, but is preferably linear from the viewpoint of ease of production.

Although the number of halogen atoms possessed by the halogenoalkyl group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more from the viewpoint of solubility. From the viewpoint of compatibility, it is preferably 7 or less, more preferably 6 or less, and even more preferably 5 or less.

Specific examples of halogenoalkyl groups include 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,4,4,5,5-octa Examples include a fluoropentyl group and the like, and among these, a 2,2,3,3-tetrafluoropropyl group is more preferable from the viewpoint of ease of production.
Examples of the substituent that the halogenoalkyl group may have include a hydroxyl group and an alkoxy group, and from the viewpoint of ease of production, it is preferably unsubstituted.

X represents a direct bond or a carbonyl group, preferably a direct bond from the viewpoint of adhesion, and preferably a carbonyl group from the viewpoint of sensitivity.
Z represents a direct bond or a carbonyl group, preferably a direct bond from the viewpoint of adhesion, and preferably a carbonyl group from the viewpoint of sensitivity.

Specific examples of the oxime ester compound represented by the general formula (I) include the following.

The (c) photopolymerization initiator in the photosensitive coloring composition of the present invention contains the oxime ester compound represented by the general formula (I), and further contains other photopolymerization initiators. good too.

Other photopolymerization initiators include, for example, Japanese Patent Laid-Open No. 59-152396, metallocene compounds containing titanocene compounds described in Japanese Patent Laid-Open No. 61-151197; Japanese Patent Laid-Open No. 2000-56118. hexaarylbiimidazole derivatives described in publications; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl-α-amino acids such as N-phenylglycine described in Japanese Patent Laid-Open No. 10-39503; Radical activators such as N-aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; JP-A-2000-80068, JP-A-2006-36750 , International Publication No. 2008/075564, International Publication No. 2009/131189, and the like.

A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
For the purpose of increasing sensitivity, the photopolymerization initiator can be blended with a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary. Examples of sensitizing dyes include the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. 3-Ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyrromethenes described in JP-A-6-19240. Dyes, other, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69 , JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818 having a dialkylaminobenzene skeleton described in A dye etc. can be mentioned.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone , benzophenone compounds such as 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5 ] benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl ) benzothiazole, 2-(p-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-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine and p-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl)pyrimidine. Among these, the most preferred is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may also be used singly or in combination of two or more.

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

<(d) ethylenically unsaturated compound>
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (d) Sensitivity is improved by including an ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in its molecule. Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, and a carboxylic acid having one ethylenically unsaturated bond, a polyhydric or monohydric alcohol monoester, and the like. mentioned.

In the present invention, it is particularly preferred to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less. Yes, more preferably 7 or less. When the concentration is equal to or higher than the lower limit, there is a tendency for the sensitivity to be high, and when the concentration is equal to or lower than the upper limit, the solubility in a solvent tends to be improved.

Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic poly Esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a hydroxy compound and an unsaturated carboxylic acid or a polybasic carboxylic acid are included.

Esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters obtained by replacing the acrylates of these exemplary compounds with methacrylates Similarly, itaconate instead of itaconate, crotonate instead of clonate, maleate instead of maleate, and the like.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. etc.

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

Other examples of polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester. Urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful.

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

Among these, it is preferable to use (meth)acrylic acid alkyl ester as the (d) ethylenically unsaturated compound from the viewpoint of curability, 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 the present invention contains (e) a solvent. (e) By including a solvent, the pigment can be dispersed in the solvent, and coating is facilitated.
The photosensitive coloring composition of the present invention usually comprises (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and necessary Various other materials are used in a state of being dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coatability.

Among the organic solvents, it is preferable to select one having a boiling point in the range of 100 to 300° C., more preferably one having a boiling point in the range of 120 to 280° C., from the viewpoint of coating properties. In addition, the boiling point here means the boiling point at a pressure of 1013.25 hPa.

Examples of such organic solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Glycol monoalkyl ethers such as monoethyl ether, tripropylene glycol methyl ether;

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

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

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

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 ketone, methyl nonyl ketone, methoxymethyl pentanone ketones;

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

Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, γ-butyrolactone;

Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile;

Commercially available organic solvents corresponding to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco 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 shall apply hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any are also trade names).
These organic solvents may be used alone or in combination of two or more.

When a colored spacer is formed by photolithography, it is preferable to select an organic solvent having a boiling point within the range of 100 to 200° C. (at a pressure of 1013.25 hPa. Hereinafter, all boiling points are the same.). More preferably, it has a boiling point of 120-170°C.

Among the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of applicability, surface tension, etc., and relatively high solubility of constituent components in the composition.
Also, the glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as organic solvents to be used in combination.

Among them, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the colored resin composition to be obtained later tends to decrease, resulting in a decrease in storage stability. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 150° C. or higher (hereinafter sometimes referred to as a “high boiling point solvent”). By using such a high boiling point solvent in combination, the photosensitive coloring composition becomes difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying.

That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to the deposition and solidification of the coloring material at the tip of the slit nozzle. Among the various solvents described above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred because of their high effect.

The content of the high-boiling solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. By setting the temperature to the above lower limit or higher, for example, it tends to be possible to suppress the deposition and solidification of the coloring material at the tip of the slit nozzle, thereby causing foreign matter defects. It tends to suppress problems such as poor tact in the vacuum drying process and pin marks in the pre-bake process.

The high boiling solvent having a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling solvent having a boiling point of 150°C or higher is separately contained. It doesn't matter if you don't.

Examples of preferred high-boiling solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and 1,6-hexanol diacetate. Acetate, triacetin and the like.

<(f) Dispersant>
The photosensitive coloring composition of the present invention contains (f) a dispersant, since it is important to finely disperse (a) the coloring agent and stabilize the dispersion state in order to ensure quality stability. .

(f) As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary Polymeric dispersants having functional groups such as amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred.

Above all, polymeric dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine disperse pigments. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of dispersant.

Examples of polymeric dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of a monomer having an amino group and a macromonomer, and polyoxyethylene alkyl ethers. Examples include system dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such dispersants include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and SOLSPERSE. (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.).
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.

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

Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK 160-166, 182 series (all of which are urethane-based), DISPERBYK 2000, 2001, LPN21116, etc. (all of which are acrylic-based) (all of which are manufactured by BYK-Chemie).

A specific example of a preferred chemical structure as a urethane polymer dispersant is, for example, a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule. Dispersion resins having a weight-average molecular weight of 1,000 to 200,000 obtained by reacting a compound having an active hydrogen and a tertiary amino group in the molecule can be used. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted to quaternary ammonium bases.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω Alicyclic diisocyanates such as ′-diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thiophosphate and triisocyanates such as triisocyanates, trimers thereof, water adducts, and polyol adducts thereof.

Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the above-mentioned polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part After the trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Compounds having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has a carbon number. Examples include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more of these.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of

Polyetherester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, e.g. oxytetramethylene) adipate and the like.

The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 ,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic glycols; bishydroxymethylcyclohexane and other aliphatic glycols; aromatic glycols such as lenglycol and bishydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine; , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol, polymethylvalerolactone and these Mixtures of two or more are included. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. is mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

The compound having one or two hydroxyl groups in the same molecule generally has a number average molecular weight of 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be explained.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of the amino group of is preferred.

The tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.

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

Further, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes a pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo 5-membered nitrogen-containing hetero ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring; 6-membered nitrogen-containing hetero ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring ring. Preferred among these nitrogen-containing heterocycles are imidazole rings and triazole rings.

Specific examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole and the like.

Specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 ,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.

Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable.
These may be used individually by 1 type, and may use 2 or more types together.

A preferred blending ratio of raw materials for producing a urethane-based polymer dispersant is 10 parts by mass of a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule per 100 parts by mass of a polyisocyanate compound. to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3, of a compound having active hydrogen and a tertiary amino group in the same molecule ~24 parts by mass.

The urethane polymer dispersant is produced according to a known method for producing polyurethane resins. Solvents used in the production generally include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane. Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.

A urethanization reaction catalyst is usually used for the above production. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; class amines, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably, it is in the range of 5-95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. If the amine value is lower than the above range, the dispersibility tends to be lowered, and if it exceeds the above range, the developability tends to be lowered.

When the isocyanate group remains in the polymer dispersant after the reaction described above, it is preferable to crush the isocyanate group with an alcohol or an amino compound, since the stability of the product over time increases.
The weight-average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered, the dispersibility is poor, and control of the reaction becomes difficult.

As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use random copolymers, graft copolymers and block copolymers with unsaturated group-containing monomers having no functional groups. These copolymers can be produced by known methods.

Examples of unsaturated group-containing monomers having functional groups include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acrylic acid, royloxyethyl hexahydrophthalic acid, unsaturated monomers having a carboxyl group such as acrylic acid dimer, tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternary products thereof, Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used individually by 1 type, and may use 2 or more types together.

Examples of unsaturated group-containing monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N - N-substituted maleimides such as benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly 2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples include macromonomers such as caprolactone macromonomers. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may contain a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group. may be contained in the A block in any form of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.

The AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Of these, in the anionic living polymerization method, the polymerization active species is an anion, and is represented by, for example, the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are integers of 1 or more.

In the radical living polymerization method, the polymerization active species is a radical, and is shown, for example, in the scheme below.

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

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

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

Such a block copolymer may usually contain an amino group generated during the production process, and the amine value thereof is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, It is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.

Here, the amine value of dispersants such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol/L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.

Amine value [mgKOH/g] = (561 x V)/(W x S)
[However, W: Amount of weighed dispersant sample [g], V: Amount of titration [mL] at the end point of titration, S: Solid content concentration [% by mass] of dispersant sample. ]

In addition, the amine value of this block copolymer depends on the presence and type of the acidic group that is the source of the acid value, but is generally preferably lower, usually 10 mgKOH/g or less, and its weight average molecular weight (Mw ) is preferably in the range of 1000 to 100,000. Within the above range, there is a tendency to ensure good dispersibility.

When having a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as "repeating (sometimes referred to as unit (i)”).

In the above formula (i), each of R ³¹ to R ³³ is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted and two or more of R ³¹ to R ³³ may combine with each other to form a cyclic structure. ^R34 is a hydrogen atom or a methyl group. X is a divalent linking group and Y ^- is a counter anion.

The number of carbon atoms in the optionally substituted alkyl group in R ³¹ to R ³³ of formula (i) is not particularly limited, but is usually 1 or more and preferably 10 or less, and 6 The following are more preferable.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

The number of carbon atoms in the optionally substituted aryl group in R ³¹ to R ³³ of formula (i) is not particularly limited, but is usually 6 or more and preferably 16 or less, and 12 The following are more preferable.

Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms in the optionally substituted aralkyl group in R ³¹ to R ³³ of formula (i) is not particularly limited, but is usually 7 or more and preferably 16 or less, and 12 The following are more preferable.

Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropyl group and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

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

Further, when the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as "repeating unit (ii)" .).

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted R ³⁵ and R ³⁶ may combine with each other to form a cyclic structure. ^R37 is a hydrogen atom or a methyl group. Z is a divalent linking group.

As the optionally substituted alkyl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ³³ in the above formula (i) can be preferably employed. can.
Similarly, as the optionally substituted aryl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ³³ in the above formula (i) are preferably employed. can be done. As the optionally substituted aralkyl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ³³ in the above formula (i) can be preferably employed. can.

Among these, R ³⁵ and R ³⁶ are preferably each independently an optionally substituted alkyl group, more preferably a methyl group or an ethyl group.

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

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R ⁴³ — group, —COOR ⁴⁴ — group [provided that R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms] and the like, which are preferred. is a —COO—R ⁴⁴ — group.
In the above formula (i), examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ and the like.

The content ratio of the repeating unit represented by formula (i) is not particularly limited. From the viewpoint of dispersibility, it is preferably 60 mol% or less with respect to the total content of the repeating unit represented by the formula (i) and the content of the repeating unit represented by the formula (ii), and more It is preferably 50 mol % or less, more preferably 40 mol % or less, and particularly preferably 35 mol % or less. Also, it is preferably 5 mol % or more, more preferably 10 mol % or more, still more preferably 20 mol % or more, and particularly preferably 30 mol % or more.

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

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

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

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

Although the number of carbon atoms in the optionally substituted alkyl group in R ⁴¹ of formula (iii) is not particularly limited, it is usually 1 or more, preferably 2 or more. Also, it is preferably 10 or less, more preferably 6 or less.

Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

Further, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, from the viewpoint of compatibility and dispersibility in a binder component such as a solvent. Also, it is preferably 10 or less, more preferably 5 or less.

In addition, the content ratio of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol % or more, and preferably 2 mol % or more. More preferably, it is 4 mol % or more. Also, it is preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less. Within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability.

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

In formula (iv) above, R ³⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. ^R39 is a hydrogen atom or a methyl group.

The number of carbon atoms in the optionally substituted alkyl group in R ³⁸ of formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 4 or more. more preferred. Also, it is preferably 10 or less, more preferably 8 or less.

Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

Although the number of carbon atoms in the optionally substituted aryl group in R ³⁸ of formula (iv) is not particularly limited, it is usually 6 or more. Also, it is preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less.

Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

Although the number of carbon atoms in the optionally substituted aralkyl group in R ³⁸ of the formula (iv) is not particularly limited, it is usually 7 or more, preferably 16 or less, and 12 or less. is more preferable, and 10 or less is even more preferable.

Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropyl group and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethylene group.

Examples of the substituent that the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Further, examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group, and the like. The chain alkyl group represented by R ³⁸ includes both straight chain and branched chain alkyl groups.

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

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

From the viewpoint of further increasing the dispersibility, the polymer dispersant includes an A block having the repeating unit (i) and the repeating unit (ii) and a B block having no repeating unit (i) and the repeating unit (ii) and is preferably a block copolymer.

The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Introducing not only a quaternary ammonium base but also a tertiary amino group into the A block unexpectedly tends to significantly improve the dispersing ability of the dispersant. Also, the B block preferably has the repeating unit (iii), and more preferably has the repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization or block copolymerization. Two or more kinds of repeating units (i) and repeating units (ii) may be contained in one A block. It may be contained in any mode of block copolymerization.

In addition, repeating units other than repeating units (i) and repeating units (ii) may be contained in the A block. Repeating units derived from mers and the like are included. The content of repeating units other than repeating units (i) and repeating units (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in a block.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block. 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-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Examples thereof include repeating units derived from monomers such as ether; N-methacryloylmorpholine.

The content of repeating units other than repeating units (iii) and repeating units (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and such repeating units are B Most preferably it is not contained in a block.

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

<Other ingredients of the photosensitive coloring composition>
In addition to the components described above, the photosensitive coloring composition of the present invention contains an adhesion improver such as a silane coupling agent, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment derivative. etc. can be appropriately blended.

(1) Adhesion Improver The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve adhesion to a substrate. As the adhesion improver, silane coupling agents, phosphoric acid group-containing compounds, and the like are preferable.
As for the types of silane coupling agents, epoxy, (meth)acrylic, amino, and the like can be used singly or in combination of two or more.

Preferred silane coupling agents include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. , epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples include isocyanate silanes such as 3-isocyanatopropyltriethoxysilane, and particularly preferred are silane coupling agents of epoxysilanes.
As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.

In general formulas (g1), (g2) and (g3) above, 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.
One type of these phosphoric acid group-containing compounds may be used alone, or two or more types may be used in combination.

(2) Surfactant The photosensitive coloring composition of the present invention may contain a surfactant in order to improve coating properties.

Various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used as the surfactant. Among them, it is preferable to use nonionic surfactants because they are less likely to adversely affect various properties. Among them, fluorine-based or silicon-based surfactants are effective in terms of coatability.

Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (Shin-Etsu Silicone company), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicone Co., Ltd.), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar) ), FC4430 (manufactured by Sumitomo 3M) and the like.
In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and ratios.

(3) Pigment Derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.
Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine. Among them, phthalocyanine-based and quinophthalone-based derivatives are preferred.

Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be directly attached to the pigment skeleton or may be attached to the skeleton of the pigment. Examples thereof include those bonded via a ring group or the like, preferably a sulfonic acid group. A single pigment skeleton may be substituted with a plurality of these substituents.

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

(4) Photo-acid generator A photo-acid generator is a compound that can generate an acid when exposed to ultraviolet light. Cross-linking reaction will proceed.

Among such photoacid generators, those having high solubility in solvents, particularly those used in photosensitive coloring compositions, are preferred. For example, diphenyliodonium, ditolyliodonium, phenyl(p-anisyl)iodonium, bis(m-nitrophenyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p-chlorophenyl)iodonium, bis(n-dodecyl) ) iodonium, diaryliodonium such as p-isobutylphenyl(p-tolyl)iodonium, p-isopropylphenyl(p-tolyl)iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide or borofluoride, hexafluoro Phosphate salts, hexafluoroarsenate salts, aromatic sulfonates, tetrakis(pentafluorophenyl)borate salts, and sulfonium organic boron complexes such as diphenylphenacylsulfonium (n-butyl)triphenylborate, or 2 Triazine compounds such as -methyl-4,6-bistrichloromethyltriazine and 2-(4-methoxyphenyl)-4,6-bistrichloromethyltriazine can be mentioned, but not limited thereto.

(5) Cross-linking agent The photosensitive coloring composition of the present invention may further contain a cross-linking agent such as a melamine or guanamine compound. Examples of these cross-linking agents include melamine- or guanamine-based compounds represented by the following general formula (6).

In formula ⁽ 6 ^{) ,} R ^{61 represents} a -NR ⁶⁶ R ^{67 group} or an aryl group having 6 ^to 12 carbon atoms ^; , one of R ⁶⁶ and R ⁶⁷ , and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group, and R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and the rest of R ⁶⁷ independently represent hydrogen or a —CH ₂ OR ⁶⁸ group, where R ⁶⁸ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. show.

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 and naphthyl groups include alkyl groups, alkoxy groups, halogen atoms and the like. may be bonded. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

Melamine-based compounds corresponding to general formula (6), that is, compounds of the following general formula (6-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxy Methylmelamine, hexaethoxymethylmelamine and the like are included.

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 group, and the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ is a hydrogen atom or represents an alkyl group.

Further, guanamine compounds corresponding to general formula (6), that is, compounds in which R ⁶¹ in general formula (6) is aryl, include tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, and tetraethoxymethylbenzoguanamine. etc. are included.

Furthermore, a cross-linking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below.

2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl)perhydro-1,3 ,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethylene urea or its dimethyl ether, 3,5-bis(hydroxymethyl)perhydro-1,3,5- Oxadiazin-4-one (commonly known as dimethyloluron) or its dimethyl ether derivative, tetramethylolglyoxaldiurein or its tetramethyl ether derivative.

In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the cross-linking agent used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

(6) Mercapto compound A mercapto compound can be added as a polymerization accelerator and for improving adhesion to the substrate.

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropio pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyrate) aryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate) , butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine- Mercapto compounds having a heterocyclic ring such as 2,4,6(1H,3H,5H)-trione or aliphatic polyfunctional mercapto compounds are included. These various things can be used individually by 1 type, or in mixture of 2 or more types.

<Amount of components in photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content of (a) the coloring agent is usually 10% by mass or more, preferably 20% by mass or more, relative to the total solid content in the photosensitive coloring composition. , and more preferably 30% by mass or more. In addition, it is usually preferably 60% by mass or less, more preferably 50% by mass or less.

(a) When the content of the colorant is at least the above lower limit, there is a tendency to obtain a sufficient optical density (OD), and when it is at most the above upper limit, it is easy to obtain sufficient plate-making properties. Tend.

In the first aspect and the fourth aspect, (a) at least one pigment selected from the group consisting of red pigments and orange pigments is preferably 1 part by mass or more with respect to 100 parts by mass of the colorant, It is more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. Further, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and 7 parts by mass or less. is particularly preferred. When the content is at least the above lower limit, a sufficient optical density (OD) tends to be obtained, and when the content is at most the above upper limit, plate-making properties tend to be secured.

In the first aspect and the fourth aspect, (a) at least one pigment selected from the group consisting of blue pigments and violet pigments is preferably 20 parts by mass or more with respect to 100 parts by mass of the colorant, It is more preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, and 65 parts by mass or more. Most preferably there is. Also, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, and particularly preferably 70 parts by mass or less. When the content is equal to or higher than the lower limit, light-shielding properties tend to be ensured, and when the content is equal to or lower than the upper limit, plate-making properties tend to be ensured.

In the second aspect, (a) the content of the organic black pigment represented by the general formula (1) with respect to 100 parts by mass of the colorant is preferably 5 parts by mass or more, and is preferably 10 parts by mass or more. more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, particularly preferably 60 parts by mass or more, most preferably 70 parts by mass or more . Also, it is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 85 parts by mass or less, and particularly preferably 80 parts by mass or less. The lower limit value or more tends to improve the light-shielding property, and the upper limit value or less tends to suppress a decrease in reliability.

In the third aspect, the organic pigment is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and preferably 60 parts by mass or more based on 100 parts by mass of the (a) colorant. More preferably, it is particularly preferably 70 parts by mass or more. Further, it is preferably 99 parts by mass or less, more preferably 95 parts by mass or less, even more preferably 90 parts by mass or less, particularly preferably 85 parts by mass or less, and 80 parts by mass or less. Most preferably there is. When the content is equal to or higher than the above lower limit, plate-making properties tend to be secured, and when the content is equal to or lower than the upper limit, sufficient optical density (OD) tends to be obtained.

In the third aspect, at least one pigment selected from the group consisting of red pigments and orange pigments is preferably 0 parts by mass or more, and 1 part by mass or more, relative to 100 parts by mass of the coloring agent (a). It is more preferable that the amount is 2 parts by mass or more. Further, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and 0 parts by mass. is most preferred. When the content is at least the above lower limit, a sufficient optical density (OD) tends to be obtained, and when the content is at most the above upper limit, plate-making properties tend to be secured.

In the third aspect, (a) at least one pigment selected from the group consisting of blue pigments and purple pigments is preferably 20 parts by mass or more, and preferably 30 parts by mass or more, with respect to 100 parts by mass of the coloring agent. more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, most preferably 65 parts by mass or more . Also, it is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less. When the content is equal to or higher than the lower limit, light-shielding properties tend to be ensured, and when the content is equal to or lower than the upper limit, plate-making properties tend to be ensured.

(a) When the colorant contains an organic black pigment, the organic black pigment is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 20 parts by mass with respect to 100 parts by mass of the colorant (a) More preferably, it is at least 1 part. Also, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less. When the content is at least the above lower limit, a sufficient optical density (OD) tends to be obtained, and when the content is at most the above upper limit, plate-making properties tend to be secured.

(a) When the colorant contains carbon black, the amount of carbon black for 100 parts by mass of the (a) colorant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 15 parts by mass or more. More preferably, it is more preferably 20 parts by mass or more. Also, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less. When the content is at least the above lower limit, a sufficient optical density (OD) tends to be obtained, and when the content is at most the above upper limit, plate-making properties tend to be secured.

(b) The content of the alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 20% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. is 25% by mass or more, particularly preferably 30% by mass or more. It is usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

(b) By setting the content of the alkali-soluble resin to the above lower limit or more, there is a tendency that the solubility of the unexposed portion in the developing solution is suppressed, and the poor development can be suppressed. Further, by making it equal to or less than the above upper limit, it is possible to suppress an increase in permeability of the developing solution into the exposed area, and there is a tendency to suppress a decrease in sharpness and adhesion of pixels.

(c) The content of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, relative to the total solid content of the photosensitive coloring composition of the present invention. , more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. It is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 7% by mass or less.

(c) When the content of the photopolymerization initiator is equal to or higher than the above lower limit, there is a tendency to suppress a decrease in sensitivity. , there is a tendency that poor development can be suppressed.

(c) The content of the oxime ester compound represented by the general formula (I) contained in the photopolymerization initiator is not particularly limited, but is usually 10% by mass or more, preferably 30% by mass or more, more preferably It is 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass or less. By making it more than the said lower limit, there exists a tendency for the surface smoothness of the hardened|cured material obtained to become favorable.

(c) When a polymerization accelerator is used together with the photopolymerization initiator, the content of the polymerization accelerator is preferably 0.05% by mass or more based on the total solid content of the photosensitive coloring composition of the present invention, and usually It is 10% by mass or less, preferably 5% by mass or less, and the polymerization accelerator is usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass based on 100 parts by mass of the photopolymerization initiator (c). It is preferable to use them in proportions.

By setting the content of the polymerization accelerator to the above lower limit or more, there is a tendency to suppress the decrease in sensitivity to exposure light, and by setting the content to the above upper limit or less, the decrease in the solubility of the unexposed portion in the developer is suppressed. and tend to be able to suppress poor development.
Further, the blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 20% by weight or less, preferably 15% by weight or less, and further the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. Preferably, it is 10% by mass or less.

(d) The content of the ethylenically unsaturated compound is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total solid content of the photosensitive coloring composition of the present invention. (d) By setting the content ratio of the ethylenically unsaturated compound to the above upper limit or less, it is possible to suppress an increase in the permeability of the developer into the exposed area and to easily obtain a good image. be. The lower limit of the content of (d) the ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more.

In addition, the photosensitive coloring composition of the present invention has a solid content concentration of usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 30% by mass, by using (e) a solvent. The solution is prepared so that it becomes less than mass %.

(f) The content of the dispersant is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more in the solid content of the photosensitive coloring composition. In addition, it is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

In addition, the content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less, especially It is preferably 30 parts by mass or less.

(f) By setting the content ratio of the dispersant to the above lower limit or more, there is a tendency that sufficient dispersibility can be easily obtained, and by setting it to the above upper limit or less, the ratio of other components is relatively reduced. It tends to be possible to suppress deterioration in sensitivity, plate-making properties, and the like.

When using an adhesion improver, the content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4, based on the total solid content in the photosensitive coloring composition. ~2% by mass. When the content of the adhesion improver is at least the above lower limit, there is a tendency that a sufficient effect of improving adhesion can be obtained. There is a tendency that it can be suppressed that it becomes a defect.

Further, when a surfactant is used, the content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0, based on the total solid content in the photosensitive coloring composition. 0.01-0.5% by weight, most preferably 0.03-0.3% by weight. When the surfactant content is at least the above lower limit, the coating film tends to exhibit smoothness and uniformity, and when it is at or below the above upper limit, the coating film exhibits smoothness and uniformity. It tends to be easy and suppress the deterioration of other properties.

<Physical properties of photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a colored spacer, and from the viewpoint of use as a colored spacer, it preferably exhibits a black color. Further, the optical density (OD) per 1 μm of film thickness of the coating film is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, and 1 0.8 or more is particularly preferred. It is usually 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less.

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition (hereinafter sometimes referred to as "resist") of the present invention is produced according to a conventional method.
Generally, (a) the colorant is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the coloring agent (a) is finely divided by the dispersing treatment, the coating properties of the resist are improved.

Dispersion treatment is usually preferably carried out in a system using a combination of (a) a colorant, (e) a solvent, (f) a dispersant, and (b) a part or all of an alkali-soluble resin (hereinafter referred to as dispersion The mixture subjected to the treatment and the composition obtained by the treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymeric dispersant as (f) the dispersant, since the thickening of the resulting ink and resist over time is suppressed (they are excellent in dispersion stability).

Thus, in the process of producing a resist, it is preferable to produce a pigment dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) organic solvent, and (f) dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive coloring composition are preferably employed. can be done.

When a liquid containing all the components to be blended in the photosensitive coloring composition is subjected to dispersion treatment, heat generated during the dispersion treatment may denature highly reactive components. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersant.

When dispersing (a) the colorant with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate. The aim of dispersion is to control the glossiness of the ink so that the 20° specular glossiness (JIS Z8741) of the resist is in the range of 50-300.

If the glossiness of the resist is low, the dispersion treatment is not sufficient and coarse pigment (colorant) particles often remain, which may result in insufficient developability, adhesion, resolution, etc. . Further, if the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is crushed to produce a large number of ultrafine particles, which tends to impair the dispersion stability.

Further, the dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.

Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to form a uniform solution. In the manufacturing process of the resist, fine dust is often mixed in the liquid, so it is desirable to filter the obtained resist with a filter or the like.

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

[Colored spacer]
Next, the colored spacer using the photosensitive colored composition of the present invention will be described according to its manufacturing method.

(1) Support The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. Transparent substrates are mainly used, and the materials used include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy. Thermosetting resin sheets such as resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass can be used.

Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Besides the transparent substrate, it can also be formed on a TFT array.

In order to improve surface physical properties such as adhesiveness, the support may be subjected, if necessary, to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resins, and the like. .
The thickness of the transparent substrate is usually in the range of 0.05-10 mm, preferably 0.1-7 mm. When thin films of various resins are formed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Colored Spacer The photosensitive coloring composition of the present invention is used for the same applications as known photosensitive coloring compositions for color filters. The use as a colored spacer (black photospacer) will be described below according to a specific example of a method for forming a black photospacer using the photosensitive colored composition of the present invention.

Generally, the photosensitive coloring composition is applied in the form of a film or a pattern by a method such as coating onto a substrate on which a black photospacer is to be provided, and the solvent is dried. Subsequently, a pattern is formed by a method such as a photolithography method in which exposure and development are performed. Thereafter, black photospacers are formed on the substrate by subjecting the substrate to additional exposure and heat curing treatment, if necessary.

(3) Formation of Colored Spacer [1] Supplying Method to Substrate The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. As the method of supply, conventionally known methods such as spinner method, wire bar method, flow coating method, die coating method, roll coating method and spray coating method can be used. Alternatively, it may be supplied in a pattern by an inkjet method, a printing method, or the like.

Above all, according to the die coating method, the amount of coating liquid used is greatly reduced, and there is no effect of mist that adheres when using the spin coating method, and the generation of foreign matter is suppressed. preferable from this point of view.

The coating amount varies depending on the application, but in the case of a black photospacer, for example, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. Also, it is important that the dry film thickness or the height of the finally formed spacers is uniform over the entire substrate. If the variation is large, a mura defect will occur in the liquid crystal panel.

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

As the substrate, a known substrate such as a glass substrate can be used. Moreover, it is preferable that the substrate surface is flat.

[2] Drying Method Drying after supplying the photosensitive coloring composition solution onto the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven. Alternatively, a reduced pressure drying method, in which drying is performed in a reduced pressure chamber without raising the temperature, may be combined.

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

[3] Exposure method Exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet light or visible light through this mask pattern. When performing exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or placing the exposure mask at a position away from the coating film of the photosensitive coloring composition, the exposure A method of projecting exposure light through a mask may also be used. Alternatively, a scanning exposure method using a laser beam without using a mask pattern may be used.

At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, the exposure is performed in an oxygen-free atmosphere, or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. You can

As a preferred embodiment of the present invention, when black photospacers having different heights are simultaneously formed by a photolithographic method, for example, a light shielding portion (light transmittance of 0%) and a plurality of openings having the highest average light transmittance are used. An exposure mask is used that has openings with a small average light transmittance (intermediate transmission openings) relative to high openings (perfect transmission openings). According to this method, the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the amount of exposure, causes the difference in the residual film ratio.

For example, a method of forming the intermediate transmission aperture by a matrix-shaped light shielding pattern having minute polygonal light shielding units is known. Also known is a method of controlling the light transmittance by using a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material as an absorber.

The light source used for the above exposure is not particularly limited. Examples of light sources 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, and fluorescent lamps, argon ion lasers, YAG lasers, Examples include laser light sources such as excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. An optical filter can also be used when using it by irradiating the light of a specific wavelength.

The optical filter may be, for example, a thin film type capable of controlling the light transmittance at the exposure wavelength. MoSi, Si, W, Al, etc. are mentioned.

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

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

Alkaline compounds 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, inorganic alkaline compounds such as ammonium hydroxide, mono-/di- or triethanolamine, mono-/di- or trimethylamine , mono-/di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-/di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), organic alkaline such as choline compound. These alkaline compounds may be a mixture of two or more.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts; and amphoteric surfactants such as alkylbetaines and amino acids.

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

The conditions for the development treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50°C, especially 15 to 45°C, particularly preferably 20 to 40°C. Any method such as a development method or an ultrasonic development method can be used.

[5] Post-exposure and heat curing treatment If necessary, the substrate after development may be subjected to post-exposure in the same manner as the exposure method described above, or may be subjected to heat curing treatment. At this time, the heat curing treatment conditions are such that the temperature is selected in the range of 100° C. to 280° C., preferably 150° C. to 250° C., and the time is selected in the range of 5 minutes to 60 minutes.

The size, shape and the like of the colored spacer of the present invention are appropriately adjusted depending on the specifications of the color filter to which it is applied. It is useful for simultaneously forming black photospacers with different heights, in which case the height of the spacer is usually about 2-7 μm, and the sub-spacer is usually about 0.2-1.5 μm lower than the spacer. have

In addition, the optical density (OD) per 1 μm of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more, from the viewpoint of light-shielding properties. Moreover, it is usually 4.0 or less, preferably 3.0 or less. Here, the optical density (OD) is a value measured by the method described later.

[Color filter]
The color filter of the present invention comprises the colored spacer of the present invention as described above. are laminated to form a colored spacer, and then an alignment film is formed.

A liquid crystal cell is formed by bonding a color filter having the colored spacer of the present invention and a substrate on the liquid crystal drive side, and a liquid crystal is injected into the formed liquid crystal cell to obtain a liquid crystal having the colored spacer of the present invention. An image display device such as a display device can be manufactured.

EXAMPLES Next, 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 as long as the gist thereof is not exceeded.
The constituent components of the photosensitive coloring compositions used in the following examples and comparative examples are as follows.

<Organic black pigment>
BASF Corporation, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))

<Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen substitution, and the temperature was raised to 120°C. Here, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and 2,2'-azobis-2-methyl 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90°C for 2 hours. Next, the inside of the reaction vessel was changed to air exchange, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100°C for 12 hours. After that, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100° C. for 3.5 hours. The alkali-soluble resin-I thus obtained had a weight average molecular weight Mw of about 8400 and an acid value of 80 mgKOH/g as measured by GPC.

<Alkali-soluble resin-II>
"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (MW = 6500, acid value = 98 mg-KOH / g)

<Dispersant-I>
"DISPERBYK-LPN21116" manufactured by BYK Chemie (A block having a quaternary ammonium base and a tertiary amino group in the side chain and a B block having no quaternary ammonium base and amino group, acrylic AB block co Polymer. Amine value: 70 mgKOH/g. Acid value: 1 mgKOH/g or less.)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. be.

<Dispersant-II>
"DISPERBYK-167" manufactured by BYK-Chemie (urethane-based polymer dispersant)

<Pigment derivative>
"Solsperse 12000" manufactured by Lubrizol
<Solvent-I>
PGMEA: propylene glycol monomethyl ether acetate <solvent-II>
MB: 3-methoxybutanol <Photoinitiator-I>
Irgacure OXE03 (manufactured by BASF)

<Photoinitiator-II>

<Photoinitiator-III>

<Photopolymerizable Monomer>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Additive>
Nippon Kayaku Co., Ltd., KAYAMER PM-21 (methacryloyl group-containing phosphate)
<Surfactant>
Megafac F-559 manufactured by DIC Corporation

<Evaluation of Optical Density (OD)>
The optical density (OD) was measured with a transmission densitometer ("D200-II" manufactured by Gretag Macbeth). Furthermore, the film thickness at the measurement points was also measured, and the optical density (unit OD) per unit film thickness (1 μm) was calculated.

<Evaluation of substrate adhesion>
Regarding the target pattern, the value of the opening diameter (μm) of the smallest opening diameter among the patterns remaining on the substrate with good resolution was defined as the minimum adhesion. The smaller this value, the better the adhesion to the substrate.

<Evaluation of surface smoothness>
For the target pattern, the occurrence of wrinkles on the surface after heating was observed with an optical microscope in a field of view of 70 μm×70 μm. The evaluation criteria are as follows.
○: Micron-order wrinkles are not observed on the pattern surface ×: Micron-order wrinkles are conspicuous on the pattern surface

<Evaluation of surface roughness>
For the target pattern, the surface roughness Sa (arithmetic mean roughness , nm) was measured.

<Preparation of Pigment Dispersion 1>
The pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent shown in Table 1 were mixed in the mass ratio shown in Table 1. This solution was subjected to dispersion treatment for 3 hours in the range of 25 to 45° C. using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a pigment dispersion liquid 1.

<Preparation of Pigment Dispersions 2 and 3>
Pigment Dispersion Liquid 2 in the same manner as Pigment Dispersion Liquid 1, except that the pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent shown in Table 1 were mixed so as to have the mass ratio shown in Table 1. and 3 were prepared.

<Pigment Dispersion 4 (Coated Carbon Black Dispersion)>
Carbon black was produced by a conventional oil furnace method. However, ethylene bottom oil with small amounts of Na, Ca, and S was used as raw material oil, and coke oven gas was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the water for stopping the reaction. 540 g of the resulting carbon black was stirred with 14,500 g of pure water using a homomixer at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container equipped with a screw-type stirrer, and while mixing at about 1,000 rpm, 600 g of toluene dissolving 60 g of epoxy resin "Epikote 828" (manufactured by Mitsubishi Chemical Corporation) was added little by little. In about 15 minutes, all of the carbon black dispersed in water migrated to the toluene side and became particles of about 1 mm.

Next, after draining with a 60-mesh wire mesh, the product was placed in a vacuum dryer and dried at 70° C. for 7 hours to completely remove toluene and water.
The obtained coated carbon black, dispersant, pigment derivative and solvent were mixed so as to have the mass ratio shown in Table 2.

This was sufficiently stirred with a stirrer for premixing. Next, dispersion treatment was performed for 6 hours at a temperature of 25 to 45° C. using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and the same mass as the dispersion liquid was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter and prepared.

[Examples 1 and 2, Comparative Examples 1 to 3]
Using the pigment dispersions 1 to 4 prepared above, each component was added so that the blending ratio shown in Table 2 was obtained, and PGMEA was added so that the solid content was 22% by mass, stirred, dissolved, and photosensitized. A coloring composition was prepared. Using the obtained photosensitive coloring composition, evaluation was performed by the method described later. The values in the upper part of Table 2 indicate the amount of each component used. On the other hand, the values in the lower row indicate the solid content of each component as a content ratio with respect to the total solid content of the photosensitive coloring composition.

<Method of collectively forming cured products with different heights>
Each photosensitive coloring composition was applied onto a glass substrate (“AN100” manufactured by AGC) using a spinner. Then, it was heated and dried on a hot plate at 100° C. for 70 seconds to form a coating film.
For the obtained coating film, a circular pattern of completely transparent openings with various diameters of 5 to 50 μm in diameter (5 to 20 μm: every 1 μm, 25 μm to 50 μm: every 5 μm) and a diameter of 5 to 50 μm (5 to 20 μm: every 1 μm) , 25 μm to 50 μm: every 5 μm), and a linear opening (complete transmission) with a width of 100 μm. The intermediate transmission aperture is a Cr oxide thin film having a light transmittance of 10±2% at a wavelength of 365 nm. The exposure gap (distance between mask and coating surface) was 220 μm. Ultraviolet light having a wavelength of 365 nm and an intensity of 32 mW/cm ² was used as light, and the exposure amount was 100 mJ/cm ² . Moreover, the ultraviolet irradiation was performed in the air.

Subsequently, using a developer consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation), the water pressure was 0 at 25 ° C. After applying shower development at 15 MPa, the development was stopped with pure water and washed with a washing spray. The shower development time was adjusted between 10 and 120 seconds and was 1.5 times the time for the unexposed coating to dissolve away.
By these operations, a pattern from which unnecessary portions were removed was obtained. The pattern-formed substrate was heated in an oven at 230° C. for 20 minutes to cure the pattern, thereby obtaining a substantially cylindrical spacer pattern.

The optical density (OD) per unit film thickness (1 μm) of the pattern corresponding to the linear aperture was measured by the method described above. In addition, substrate adhesion was evaluated by the method described above for patterns corresponding to a circular pattern of complete transmission openings of 5 to 50 μm and intermediate transmission openings of 5 to 50 μm. Furthermore, the pattern corresponding to the linear openings was evaluated for surface smoothness by the method described above. In addition, the surface roughness of the pattern corresponding to the linear opening was evaluated by the method described above. The results are shown in Table 2, respectively.

It was confirmed that the coated substrates using the photosensitive coloring compositions of Examples 1 and 2 had a high unit OD, excellent light-shielding properties, and excellent surface smoothness. Further, the substrate adhesion of the intermediate transmission opening was also good.
On the other hand, it was confirmed that Comparative Examples 1 to 3 had the same unit OD values as those of Examples 1 and 2, but had poor surface smoothness and, in addition, poor substrate adhesion at the intermediate transmission aperture.

In general, a method of increasing the pigment concentration and a method of using a pigment having a high light-shielding property in combination are known in order to improve the light-shielding property of the colored spacer. However, when such a method is applied, the ultraviolet transmittance decreases, a difference in crosslink density occurs in the film thickness direction, the crosslink density on the film surface becomes higher than that on the bottom of the film, and the film surface shrinks due to thermal shrinkage during the thermosetting process. It is thought that wrinkles are generated and the surface smoothness is deteriorated.

In the photosensitive coloring composition of the present invention, since the oxime ester compound represented by the formula (I) is used as the photopolymerization initiator, the halogen atom in the chemical structure of the compound causes the compound to form a film. The initiator tends to be distributed near the surface and is affected by oxygen inhibition, which suppresses excessive increase in cross-linking density on the film surface and reduces the occurrence of wrinkles on the film surface due to thermal shrinkage during the thermosetting process. It is considered that there is

In addition, the naphthalene ring in the carbazole skeleton of the compound increases the absorption of long-wavelength light, and the long-wavelength light contained in the ultraviolet lamp can also be used to increase the crosslink density in the vicinity of the bottom of the film. Therefore, it is considered that even a pattern formed with an opening having a low transmittance, such as an intermediate transmission opening, has good adhesion to the substrate.

[Example 3 and Comparative Example 4]
Using the pigment dispersions 3 and 4 prepared above, each component was added so that the ratio in the solid content was the mixing ratio shown in Table 3, and PGMEA was added so that the solid content was 22% by mass, and stirred. It was dissolved to prepare a photosensitive coloring composition. Using the resulting photosensitive colored composition, evaluation was performed in the same manner as in Example 1 except that the exposure dose in the exposure treatment was 40 mJ/cm ² . The values in the upper part of Table 3 indicate the amount of each component used. On the other hand, the values in the lower row indicate the solid content of each component as a content ratio with respect to the total solid content of the photosensitive coloring composition. The field of view for evaluation of surface smoothness was 5 cm×5 cm.

It was confirmed that the coated substrate using the photosensitive coloring composition of Example 3 had a high unit OD, excellent light-shielding properties, and excellent surface smoothness. Further, the substrate adhesion of the intermediate transmission opening was also good.
On the other hand, in Comparative Example 4, although the unit OD value was the same as that in Example 3, it was confirmed that the surface smoothness was poor, the surface roughness value was large, and the substrate adhesion of the intermediate transmission aperture was poor. rice field.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. It should be noted that this application is a Japanese patent application filed on March 11, 2015 (Japanese patent application 2015-048577), a Japanese patent application filed on March 11, 2015 (Japanese patent application 2015-048578), and 2015 It is based on a Japanese patent application (Japanese Patent Application No. 2015-157456) filed on August 7, which is incorporated by reference in its entirety.

According to the photosensitive coloring composition of the present invention, it is possible to provide a cured product and a colored spacer having high light-shielding properties and excellent surface smoothness, and further provide an image display device comprising such a colored spacer. be able to. Therefore, the present invention has extremely high industrial applicability in the fields of photosensitive coloring compositions, cured products, colored spacers and image display devices.

Claims (8)

A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant There is
The (a) colorant contains a compound represented by the following formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof,
The (c) photopolymerization initiator contains an oxime ester compound represented by the following formula (I),
The content of the coloring agent (a) is 10% by mass or more and 60% by mass or less with respect to the total solid content in the photosensitive coloring composition,
The photosensitive coloring composition, wherein the content of the photopolymerization initiator (c) is 2 % by mass or more and 8 % by mass or less relative to the total solid content of the photosensitive coloring composition.

(In formula (1) above, R ¹¹ and R ¹⁶ are each independently 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 independently of each other hydrogen atoms, halogen atoms, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , ^CONHR21 , ^{CONR21R22 ,} CN, ^OH , ^OR21 , ^COCR21 , _OOCNH2 , ^OOCNHR21 , ^OOCNR21R22 , _NO2 , _NH2 , ^NHR21 , ^NR21R22 , ^{NHCOR22 , NR21 COR22} , N= _CH2 , N= ^CHR21 , N= ^CR21R22 , SH, ^SR21 _, ^{SOR21 ,} _SO2R21 ^{, SO3R21} , _SO3H ^, _{SO3- , SO2NH2} , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;
and at least one combination selected from the group consisting of ^R12 and ^R13 , ^R13 and ^R14 , ^R14 and ^R15 , ^R17 and ^R18 , ^R18 and ^R19 , and ^R19 and ^R20 , directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, an NH or an 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 a carbon It is an alkynyl group of numbers 2 to 12. )

(In the above general formula (I),
R ¹ represents an aromatic ring group optionally having a substituent.
R ² represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
^R3 represents a hydrogen atom or an optionally substituted alkyl group.
^R4 represents an aromatic ring group optionally having a substituent.
R ⁵ and R ⁶ each independently represent an optionally substituted benzene ring or an optionally substituted naphthalene ring. However, at least one of R ⁵ and R ⁶ is a naphthalene ring optionally having a substituent.
At least one of R ¹ and R ⁴ has a —OR ⁷ group as a substituent. However, ^R7 represents a halogenoalkyl group.
X represents a direct bond or a carbonyl group.
Z represents a direct bond or a carbonyl group. ) The photosensitive coloring composition according to claim 1, wherein the (a) colorant contains carbon black. 3. The photosensitive coloring composition according to claim 2, wherein the content of carbon black with respect to 100 parts by mass of the coloring agent (a) is 5 parts by mass or more and 50 parts by mass or less. 4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the cured coating film has an optical density of 1.0 or more per 1 µm of film thickness. The photosensitive coloring composition according to any one of claims 1 to 4, which is used for collectively forming colored spacers having different heights by photolithography. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 5. A colored spacer formed from the cured product according to claim 6 . An image display device comprising the colored spacer according to claim 7 .