TWI776205B - Photosensitive colored composition - Google Patents

Abstract

An object of the present invention is to provide a photosensitive colored composition, which has a high light-blocking effect and can form a pattern having an excellent surface smoothness, and particularly is preferably used for a formation of a colored spacer. The photosensitive colored composition for colored spacer formation of the present invention comprises (a) a coloring agent, (b) an alkali soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, wherein the photopolymerization initiator (c) contains an oxime ester compound represented by the following formula (I) :

Description

Photosensitive coloring composition

The present invention relates to a photosensitive coloring composition and the like. Specifically, for example, it relates to a photosensitive coloring composition preferably used for forming coloring spacers and the like in color filters such as liquid crystal displays, a coloring spacer obtained by curing the photosensitive coloring composition, and the The image display device of the coloring spacer.

A liquid crystal display (LCD) utilizes the property of switching the arrangement of liquid crystal molecules by switching on and off a voltage to the liquid crystal. On the other hand, most of the components constituting the LCD unit are formed by a method using a photosensitive composition represented by a photolithography method. Since this photosensitive composition is easy to form a fine structure, it is also easy to handle the substrate for large screens, and the like, the application range thereof tends to be further expanded in the future.

However, the LCD manufactured using the photosensitive composition cannot maintain the voltage applied to the liquid crystal due to the electrical properties of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition, resulting in the display of the display. Cases of inequality problems. Especially in the color liquid crystal display, the components closer to the liquid crystal layer, such as the so-called column spacers and optical spacers, which are used to maintain a constant interval between two substrates in the liquid crystal panel, have a great influence.

In the past, when a spacer having no light-shielding property was used in a thin-film transistor (TFT) type LCD, there was a switching element. A case where the TFT malfunctions due to light passing through the spacer. In order to prevent this, for example, Patent Document 1 describes a method of using a spacer (colored spacer) having light-shielding properties.

On the other hand, in recent years, with the change of the panel structure, a method of forming coloring spacers having different heights at one time by a photolithography method has been proposed. For example, Patent Document 2 discloses that by combining several specific types of pigments with different light absorption properties, the balance of light absorption in the ultraviolet region and the visible light region can be ensured, the light-shielding property and the voltage holding ratio of the liquid crystal can be maintained, and Control of shape or level difference, and adhesion to the substrate are realized. In addition, Patent Document 3 discloses that a plurality of organic color pigments are used as pigments, and Patent Document 4 discloses that an organic black pigment is used.

On the other hand, in patent document 5, in order to improve curability, it is described that a specific oxime ester compound is used as a high-sensitivity photopolymerization initiator in the use of a color filter photoresist.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 8-234212

Patent Document 2: International Publication No. 2013/115268

Patent Document 3: Korean Registered Patent Publication No. 10-1266295

Patent Document 4: Japanese Patent Publication No. 2014-529652

Patent Document 5: Japanese Patent Publication No. 2014-500852

In recent years, with the change of panel structure, further improvement of coloring is required. Shading properties of spacers. As a method of improving light-shielding property, the method of using the pigment with high light-shielding property, the method of increasing the pigment content ratio in a photosensitive coloring composition, etc. are mentioned. The inventors of the present invention have found that, in the photosensitive coloring compositions described in Patent Documents 2 to 4, after the light-shielding properties of the coloring spacers are further improved by using a pigment with high light-shielding properties in combination, the photosensitive coloring compositions in the vicinity of the film surface and in the film In the vicinity of the bottom, the difference in crosslinking density becomes large, and wrinkles are generated on the surface of the coating film due to thermal shrinkage during the thermal curing process, and the surface smoothness becomes insufficient.

On the other hand, Patent Document 5 describes the use of a specific oxime ester compound as a photopolymerization initiator for a color resist. However, in Patent Document 5, there is no description or suggestion that the oxime ester compound is used as a photopolymerization initiator of a photosensitive coloring composition for forming a coloring spacer. Therefore, it is not clear what effect this oxime ester compound exhibits when it is used as a photopolymerization initiator of a photosensitive coloring composition for forming a coloring spacer.

The present invention was made in view of the above-mentioned 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.

As a result of diligent studies to solve the above-mentioned problems, the present inventors found that the above-mentioned problems can be solved by using a specific oxime ester-based compound as a photopolymerization initiator in a photosensitive coloring composition, and completed the present invention.

That is, the present invention has the following configurations of [1] to [14]. [1] A photosensitive coloring composition for forming a coloring spacer, comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, ( e) solvent and (f) dispersant, characterized in that:

The above-mentioned (c) photopolymerization initiator contains an oxime ester-based compound represented by the following formula (I).

[hua 1]

(In the above general formula (I),

R ¹ represents an aromatic ring group which may have a substituent.

R ² represents an optionally substituted alkane group or an optionally substituted aryl group.

R ³ represents a hydrogen atom or an alkyl group which may have a substituent.

R ⁴ represents an aromatic ring group which may have a substituent.

R ⁵ and R ⁶ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. Wherein, at least one of R ⁵ and R ⁶ is a naphthalene ring which may have a substituent.

At least any one of R ¹ and R ⁴ has a -OR ⁷ group as a substituent. wherein R ⁷ represents a haloalkyl group.

X represents a direct bond or a carbonyl group.

Z represents a direct bond or a carbonyl group. )

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

[3] The photosensitive coloring composition for forming a colored spacer according to [2], wherein the red pigment is the following (1), the orange pigment is the following (2), and the blue pigment is the following (3), the said purple pigment is the following (4).

(1) At least one selected from C.I. Pigment Red 177 and 254

(2) At least one selected from C.I. Pigment Orange 43 and 64

(3) At least one selected from C.I. Pigment Blue 15:6, 60

(4) At least one selected from C.I. Pigment Violet 23 and 29

[4] The photosensitive coloring composition for forming a coloring spacer according to [2] or [3], wherein at least one pigment selected from the group consisting of a red pigment and an orange pigment is relative to the above (a) The content ratio of 100 parts by mass of the colorant is 1 part by mass or more and 30 parts by mass or less.

[5] The photosensitive coloring composition for forming a coloring spacer according to any one of [2] to [4], wherein at least one pigment selected from the group consisting of a blue pigment and a violet pigment is relatively The content ratio with respect to 100 mass parts of said (a) coloring agents is 20 mass parts or more and 90 mass parts or less.

[6] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [5], wherein the (a) colorant contains an organic black pigment.

[7] The photosensitive coloring composition 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 compound thereof Salts of geometric isomers.

[hua 2]

(In the above formula (1), R ¹¹ and R ¹⁶ are 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 independently of all other groups are hydrogen atom, halogen atom, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N=CH ₂ , N=CHR ²¹ , N=CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;

And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be bonded directly to each other or bonded to each other by bridging of oxygen atoms, sulfur atoms, NH or NR ²¹ ;

R ²¹ and R ²² are independently of each other 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 cycloalkenyl group having 3 to 12 carbon atoms. Alkynyl of ~12. )

[8] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [7], wherein the (a) colorant contains carbon black.

[9] The photosensitive coloring composition for forming a colored spacer according to [1], wherein the (a) colorant 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 a red pigment, an orange pigment, a blue pigment, and a violet pigment .

[11] The photosensitive coloring composition for forming a coloring spacer according to [9] or [10], wherein the organic pigment contains at least one selected from the group consisting of (1) to (4) below kind.

(1) At least one selected from C.I. Pigment Red 177 and 254

(2) At least one selected from C.I. Pigment Orange 43 and 64

(3) At least one selected from C.I. Pigment Blue 15:6, 60

(4) At least one selected from C.I. Pigment Violet 23 and 29

[12] The photosensitive adhesive for forming a colored spacer according to any one of [9] to [11] A color composition, wherein the organic pigment contains a blue pigment and a purple pigment.

[13] The photosensitive coloring composition for forming a coloring spacer according to any one of [9] to [12], wherein the content ratio of carbon black to 100 parts by mass of the colorant (a) is 5 parts by mass part or more and 50 parts by mass or less.

[14] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [13], wherein the optical density per 1 μm of the film thickness of the coating film after curing is 1.0 or more.

[15] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [14], which is used to form colored spacers having different heights at one time 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 of the cured product described in [16].

[18] An image display device including the coloring spacer according to [17].

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive coloring composition which can form the pattern with high light-shielding property and excellent surface smoothness can be provided. Moreover, the hardened|cured material and the coloring spacer which are excellent in light-shielding property and surface smoothness can be provided, and further, the image display apparatus provided with such a coloring spacer can be provided.

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

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

In addition, in the present invention, the term "monomer" refers to the term of the so-called macromolecular substance (polymer), and means that, in addition to the narrowly defined monomer (monomer), it also includes dimer, trimer, low polymer polymer etc.

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

In the present invention, the "weight average molecular weight" refers to the weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography).

Moreover, in the present invention, the so-called "amine value" means the amine value in terms of effective solid content unless otherwise specified, and is the value represented by the mass of KOH per 1 g of base equivalent to the solid content of the dispersant. . Again, see below about the assay method. On the other hand, the so-called "acid value" means the acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.

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

[Photosensitive Coloring Composition]

The photosensitive coloring composition of the present invention contains

(a) Colorants

(b) Alkali-soluble resin

(c) Photopolymerization initiator

(d) ethylenically unsaturated compounds

(e) Solvent

(f) Dispersants

as an essential ingredient. In addition, the photosensitive coloring composition of the present invention may further contain other formulation components such as adhesion improvers such as silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, and pigment derivatives, as necessary. , usually, each formulation component is used in a state of being dissolved or dispersed in a solvent.

The photosensitive coloring composition of the present invention can form a pattern with high light-shielding properties and excellent surface smoothness, so it can be preferably used for the formation of colored spacers, that is, it can be preferably used as a photosensitive material for forming colored spacers Coloring composition.

On the other hand, properties such as light-shielding properties or surface smoothness are used in addition to coloring spacers such as spacers, especially coloring spacers (colored banks), between light-emitting portions of organic electroluminescence (EL) display devices. Since the properties are also required in other applications, it can be used not limited to the colored spacers. The photosensitive coloring composition of the present invention will be described in detail below, and unless otherwise specified, both the coloring spacer application and the application other than the coloring spacer will be described together.

In the photosensitive coloring composition according to the first aspect of the present invention, (a) the colorant contains at least one selected from the group consisting of a red pigment and an orange pigment, and a blue pigment and a purple pigment. At least 1 of the group, and (c) photopolymerization The co-starter contains an oxime ester compound represented by the following formula (I).

Moreover, in the photosensitive coloring composition according to the second aspect of the present invention, (a) the colorant contains a compound represented by the following general formula (1), its geometric isomer, its salt, or its geometric isomer. The organic black pigment of the salt of the structure (hereinafter, it may be abbreviated as "the organic black pigment represented by general formula (1)").

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

On the other hand, the photosensitive coloring composition of the 4th aspect of this invention is a photosensitive coloring composition for coloring spacer formation, and (c) the photopolymerization initiator contains the oxime ester represented by following formula (I) series compounds.

Hereinafter, unless otherwise specified, the "photosensitive coloring composition of the present invention" refers to all the photosensitive coloring compositions of the above-mentioned 1st to 4th aspects.

<(a) Colorant>

The (a) colorant used in the photosensitive coloring composition of the first aspect of the present invention contains at least one selected from the group consisting of a red pigment and an orange pigment, and a blue pigment and a violet pigment. Form at least one of the groups. Thus, the photosensitive coloring composition of the 1st aspect of this invention can achieve high light-shielding property by containing a specific organic coloring pigment.

It is preferable to use a pigment as (a) a coloring agent, and an inorganic pigment may be used as a pigment, and an organic pigment may be used. It is preferable to use an organic pigment from a viewpoint of easily suppressing the fall of a liquid crystal voltage holding ratio, and suppressing the absorption of an ultraviolet-ray, and controlling a shape and a level|step difference.

系、陰丹士林系、苝系等有機顏料以外，亦可利用各種無機顏料等。以下，以顏料編號表示可使用之顏料之具體例。以下所列舉之「C.I.顏料紅2」等用語意指顏色索引(C.I.)。 The chemical structure of these pigments is not particularly limited. For example, in addition to azo series, phthalocyanine series, quinacridone series, benzimidazolone series, isoindolinone series,

In addition to organic pigments such as indanthrene series, indanthrene series, and perylene series, various inorganic pigments can also be used. Below, the specific example of the pigment which can be used is shown by the pigment number. The terms such as "CI Pigment Red 2" listed below mean the color index (CI).

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

Among them, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 can be preferably cited, and more preferably C.I. Pigment Red 177, 209, 224, 254.

Furthermore, C.I. Pigment Red 177, 254, and 272 are preferably used in terms of dispersibility and light-shielding properties. In the case of curing the photosensitive coloring composition of the first aspect of the present invention with ultraviolet rays, it is preferable to use an ultraviolet absorber as the red pigment. lower rate. From this viewpoint, it is more preferable to use C.I. Pigment Red 254 and 272.

Examples of orange pigments include: C.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.

Among them, C.I. Pigment Orange 38 and 71 are preferably mentioned. Furthermore, C.I. Pigment Orange 43, 64, and 72 are preferably used in terms of dispersibility and light-shielding properties. When hardening the photosensitive coloring composition of the 1st aspect of this invention with an ultraviolet-ray, it is preferable to use the thing with a low ultraviolet absorptivity as an orange pigment. From this viewpoint, it is more preferable to use C.I. Pigment Orange 64 and 72.

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

Among them, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 is preferably used, and C.I. Pigment Blue 15:6 is more preferred.

Furthermore, it is preferable to use C.I. Pigment Blue 15:6, 16, 60 from the viewpoint of dispersibility and light-shielding property. When hardening the photosensitive coloring composition of the 1st aspect of this invention with an ultraviolet-ray, it is preferable to use the thing with a low ultraviolet absorptivity as a blue pigment. From this viewpoint, it is more preferable to use C.I. Pigment Blue 60.

Examples of purple pigments include: C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.

Among them, C.I. Pigment Violet 19 and 23 can be preferably cited, and more preferred are C.I. Pigment Violet 23.

Furthermore, it is preferable to use C.I. Pigment Violet 23 and 29 from the viewpoint of dispersibility and light-shielding property. When hardening the photosensitive coloring composition of the 1st aspect of this invention with an ultraviolet-ray, it is preferable to use the thing with a low ultraviolet absorptivity as a violet pigment. From this viewpoint, it is more preferable to use C.I. Pigment Violet 29.

Examples of organic coloring pigments that can be used other than red pigments, orange pigments, blue pigments, and violet pigments include green pigments, yellow pigments, and the like.

Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55. Among them, C.I. Pigment Green 7 and 36 are preferably mentioned.

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

Among them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferably cited, and C.I. Pigment Yellow 83, 138, 139, 150, 180 are more preferred.

Among these, it is preferable to contain at least 1 type or more of the following pigments from the viewpoint of light-shielding property or control of shape and level difference.

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

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

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

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

Furthermore, from the viewpoint of light-shielding properties or control of shape and level difference, the red pigment is preferably the following (1), the orange pigment is preferably the following (2), and the blue pigment is preferably the following (3) , the purple pigment is preferably the following (4).

(1) At least one selected from C.I. Pigment Red 177 and 254

(2) At least one selected from C.I. Pigment Orange 43 and 64

(3) At least one selected from C.I. Pigment Blue 15:6, 60

(4) At least one selected from C.I. Pigment Violet 23 and 29

In addition, the combination of colors is not particularly limited, and from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a blue pigment, an orange pigment and a violet can be mentioned. A combination of pigments, etc.

Furthermore, in addition to these coloring pigments, a black color material can be further used. Among the black color materials, it is preferable to use an organic black pigment, especially from the viewpoint of light-shielding properties, from the viewpoint of easily suppressing the decrease in the voltage holding ratio of the liquid crystal and controlling the shape and the level difference by suppressing the absorption of ultraviolet rays. It is preferable to use the organic black pigment which is the compound represented by following formula (1), its geometric isomer, its salt, or its salt of a geometric isomer.

[hua 3]

In formula (1), R ¹¹ and R ¹⁶ are 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 and all other groups are independently a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N=CH ₂ , N=CHR ²¹ , N=CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;

And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be bonded directly to each other or bonded to each other by bridging of oxygen atoms, sulfur atoms, NH or NR ²¹ ;

R ²¹ and R ²² are independently of each other 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 cycloalkenyl group having 3 to 12 carbon atoms. Alkynyl of ~12.

The geometric isomer of the compound represented by the general formula (1) has the following core structure (wherein, the substituent in the structural formula is omitted), and the trans-trans isomer is presumed to be the most stable.

[hua 4]

When the compound represented by the general formula (1) is anionic, it is preferably prepared by any known suitable cation, such as metal, organic, inorganic or metal-organic cations, specifically alkali metals, alkaline earth metals, Salts of transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkyl ammonium, quaternary ammonium such as tetraalkyl ammonium, or organometallic complexes to compensate for their charge. In addition, when the geometric isomer of the compound represented by the general formula (1) is anionic, it is preferably the same salt.

In the definitions of the substituents of the general formula (1) and the like, since there is a tendency that the shielding ratio becomes high, the following are preferable. The reason is that the following substituents do not have absorption and do not affect the color tone 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, and more preferably a hydrogen atom. R ¹³ and R ¹⁸ independently of each other are preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ⁻ , more preferably a hydrogen atom or SO ₃ H.

R ¹¹ and R ¹⁶ independently of each other are preferably a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom.

Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, more preferably R ¹¹ 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 .

Examples of alkyl groups having 1 to 12 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-butyl Pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethyl Hexyl, nonyl, decyl, undecyl or dodecyl.

基、

基、降蒈烷基、蒈烷基、薄荷基、降蒎基、蒎基、1-金剛烷基或2-金剛烷基。 Cycloalkyl with 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, limoneyl, normyl

base,

group, norcarenyl, carenyl, menthyl, norpinyl, pinenyl, 1-adamantyl or 2-adamantyl.

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

烯-1-基、2,5-降

二烯-1-基、7,7-二甲基-2,4-降蒈二烯-3-基或莰烯基。 Cycloalkenyl having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, and 3-cyclohexen-1-yl , 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-limone-10-yl, 2-nor

Alken-1-yl, 2,5-nor

Dien-1-yl, 7,7-dimethyl-2,4-norcaren-3-yl or camphenyl.

Examples of alkynyl groups having 2 to 12 carbon atoms are 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl , 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn- 1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn- 9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

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

The organic black pigment represented by the above general formula (1) is preferably a compound represented by the following general formula (2).

[hua 5]

Specific examples of such organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) as a trade name. The organic black pigment is preferably used by dispersing with the following dispersant, solvent, and method. Moreover, when the sulfonic acid derivative of the said general formula (2) exists at the time of dispersion|distribution, the dispersibility and storage property may improve.

Examples of black color materials 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 etc. Among these, carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics. Examples of carbon blacks include the following carbon blacks.

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

Manufactured by Degussa Corporation: Printex (registered trademark, the same below) 3, Printex30P, Printex30, Printex300P, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U , Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

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

Manufactured by Columbian Carbon: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN10004 , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As carbon black, one covered with resin can also be used. When carbon black coated with resin is used, there is an effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black covered with resin, for example, carbon black described in Japanese Patent Laid-Open No. 09-71733 can be preferably used. in terms of volume resistance or permittivity On the other hand, resin-coated carbon black is preferably used.

It is preferable that the total content of Na and Ca is 100 ppm or less as carbon black used for the coating treatment with resin. Carbon black usually contains Na or Ca, K, Mg, Al, Fe mixed with raw material oil or combustion oil (or gas) from the time of manufacture, reaction stop water or granulation water, and furnace materials of the reaction furnace, etc. and so on as the composition of ash. Among them, Na and Ca generally contain several hundred ppm or more, and by reducing these, penetration into transparent electrodes (ITO) or other electrodes tends to be suppressed and electrical short-circuiting tends to be prevented.

As a method of reducing the content of the ash containing Na or Ca, it can be achieved by carefully selecting the content of the raw material oil or fuel oil (or gas) and the reaction stop water when producing carbon black As little as possible; and minimize the amount of alkaline substances added to adjust the structure. As another method, the method of dissolving and removing Na or Ca by washing|cleaning the carbon black produced from a furnace with water, hydrochloric acid, etc. is mentioned.

Specifically, after mixing and dispersing carbon black in water, hydrochloric acid, or hydrogen peroxide water, if a poorly soluble solvent is added to the water, the carbon black moves to the solvent side and is completely separated from the water, and exists in the carbon black. Most of the Na or Ca are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use the carbon black production process of carefully selected raw materials alone or the method of dissolving with water or acid alone. By using these two methods together, it is easier to The total amount of Na and Ca is made 100 ppm or less.

In addition, the resin-coated carbon black is preferably a so-called acid carbon black having a pH of 6 or less. Since the dispersion diameter (coalescing diameter) in water becomes small, it is preferable to be able to coat fine cells. Further, the average particle diameter is preferably 40 nm or less, and the dibutyl phthalate (DBP) absorption amount is preferably 140 ml/100 g or less. By setting it within the above range, it is possible to obtain The tendency of a film with good light-shielding properties. The average particle size refers to the number-average particle size, and refers to the equivalent circle diameter obtained by particle image analysis. The particle image analysis is to take pictures taken at several fields of view and observe with an electron microscope at tens of thousands of times magnification, and About 2,000 to 3,000 particles were counted in these photos using an image processing device.

The preparation method of carbon black covered by resin is not particularly limited. For example, after appropriately adjusting the amount of carbon black and resin, the following methods can be used: 1. Mix the resin with a solvent such as cyclohexanone, toluene, and xylene, and mix The resin solution is obtained by heating and dissolving, the resin solution is mixed and stirred with a suspension obtained by mixing carbon black and water to separate the carbon black and water, and then the water is removed and heated and kneaded to obtain a composition. 2. After the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate the carbon black and resin, the obtained granules are separated and heated And remove the residual solvent and water; 3. Dissolve carboxylic acids such as maleic acid and fumaric acid in the solvent exemplified above, add and mix carbon black and dry it, remove the solvent to obtain carbon added with carboxylic acid After blackening, add resin to it and dry and blend it; 4. Mix the reactive group-containing monomer components constituting the coated resin with water at high speed to prepare a suspension, and cool it after polymerization to obtain a suspension from the polymer The reactive group-containing resin is then kneaded by adding carbon black thereto, reacting the carbon black with the reactive group (grafting the carbon black), cooling and pulverizing.

The type of resin to be coated is also not particularly limited, and is generally a synthetic resin. Furthermore, since the amphoteric surfactant of the resin having a benzene ring in its structure has a stronger effect, it is more effective in terms of dispersibility and dispersion stability. good.

As specific synthetic resins, thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glycerol resins, epoxy resins, alkyl benzene resins, etc., or polyphenylene resins can be used. vinyl, polycarbonate, parylene Polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysiloxane, poly-p-phenylene terephthalate, polyamide-imide, polyimide, polyamine-based double Maleimide, polyether polyphenylene, polyarylate, polyether ether ketone and other thermoplastic resins.

The coating amount of the resin with respect to the carbon black is preferably 1 to 30 mass % with respect to the total amount of the carbon black and the resin, and sufficient coating tends to be possible by making it more than the above lower limit value. On the other hand, by setting it below the said upper limit value, there exists a tendency for resin to be prevented from sticking and a dispersibility becomes favorable.

The carbon black coated with resin in this way can be used as a light-shielding material for coloring spacers according to a conventional method, and a color filter in which the coloring spacer is a constituent element can be produced by a conventional method. When such carbon black is used, there is a tendency that a colored spacer with a high light-shielding rate and a low surface reflectance can be achieved at a low cost. Moreover, it is also presumed that by coating the surface of the carbon black with resin, there is also an effect of encapsulating Ca or Na in the carbon black.

Moreover, dyes other than black color material can also be used for the said organic coloring pigment. Examples of dyes that can be used as color materials include azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinoneimine-based dyes, quinoline-based dyes, nitro-based dyes, carbonyl-based dyes, and methine Base dyes, etc.

Examples of azo dyes include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reaction Yellow 2, C.I. Reaction Red 17, C.I. Reaction Red 120, C.I. Reaction Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, C.I. Mordant Black 7, etc.

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

These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the reference of the average particle size is the number of pigment particles.

In addition, in the photosensitive coloring composition of the 1st aspect of this invention, the average particle diameter of a pigment is the value calculated|required from the pigment particle diameter measured by dynamic light scattering (DLS). The particle size measurement is carried out on a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005~0.2 mass %, but if it is the concentration recommended by the measuring machine, it is based on the concentration), and the temperature is 25 ℃. measurement below.

On the other hand, the (a) colorant used in the photosensitive coloring composition according to the second aspect of the present invention includes the compound represented by the above-mentioned general formula (1), its geometric isomer, its salt, or Organic black pigments of salts of its geometric isomers. In this way, it is considered that by including a specific organic black pigment, a low dielectric constant and a high light-shielding ratio can be achieved.

The (a) colorant used in the second aspect of the present invention may contain other colorants in addition to the above-mentioned organic black pigment. As other colorants, it is preferable to use a pigment, and the pigment may be either an organic pigment or an inorganic pigment, and is more preferable from the viewpoint of easily suppressing the decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to control the shape and the level difference. Use organic pigments. As the organic pigment, those listed in the first aspect can be used.

Furthermore, other black color materials can be used in addition to these pigments. Among other black color materials, it is preferable to use other organic blacks other than those represented by the above general formula (1) from the viewpoint of easily suppressing the reduction of the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to control the shape or level difference. pigment. As other organic black pigments, aniline black, perylene black, cyanine black, etc. are mentioned.

Moreover, in the 2nd aspect of this invention, an inorganic black pigment can be used. As an inorganic black pigment, carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, etc. are mentioned. Among these, carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics. As an example of carbon black, those listed in the first aspect can be used. Moreover, other color materials, such as the dye mentioned in 1st aspect, can also be used.

Moreover, the (a) coloring agent used for the photosensitive coloring composition of the 3rd aspect of this invention contains an organic pigment and carbon black. In this way, by using an organic pigment that absorbs less ultraviolet rays, it is easy to control the shape or level difference; and by using carbon black in addition to the organic pigment, high light-shielding properties can be achieved.

The type of the organic pigment is not particularly limited, but from the viewpoint of adhesiveness, it is preferable to contain at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment, and a violet pigment. As the red pigment, orange pigment, blue pigment, and purple pigment, those listed in the first aspect can be used.

Among these, it is preferable to contain at least 1 type or more of the following (1)-(4) from a light-shielding property, or the viewpoint of the control of a shape and a level|step difference.

(1) At least one selected from C.I. Pigment Red 177 and 254

(2) At least one selected from C.I. Pigment Orange 43 and 64

(3) At least one selected from C.I. Pigment Blue 15:6, 60

(4) At least one selected from C.I. 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 light region, especially in the long wavelength region. In particular, in the absorption spectrum of carbon black, the absorbance decreases to the right from short wavelengths to long wavelengths, and the absorbance in the ultraviolet region is also higher than that of organic pigments. Therefore, from the viewpoint of both light-shielding properties and plate-making properties, it is preferable to use them together. Blue pigment and/or violet pigment and carbon black, more preferably blue pigment, violet pigment and carbon black are used together.

Moreover, it is preferable that an organic pigment contains an organic black pigment from a light-shielding viewpoint. As the organic black pigment, those listed in the first aspect can be used. Moreover, other organic coloring pigments listed in the 1st aspect, or other black color materials, dyes, etc. can also be used.

Moreover, the (a) coloring agent used in the photosensitive coloring composition for coloring spacer formation of the 4th aspect of this invention will not be specifically limited if it can form a desired coloring spacer. For example, from the viewpoint of easily suppressing the absorption of ultraviolet rays and controlling the shape and the level difference, it is preferable to contain at least one selected from the group consisting of a red pigment and an orange pigment as the first aspect described above. species, and at least one selected from the group consisting of blue pigments and purple pigments.

In this way, as the colorant (a) used in the photosensitive coloring composition for forming a colored spacer of the fourth aspect, the colorant (a) used in the photosensitive coloring composition of the first aspect can be applied In addition, what is described can also be applied and described as the (a) coloring agent used in the photosensitive coloring composition of the 2nd or 3rd aspect.

On the other hand, in the photosensitive coloring composition for coloring spacer formation of the 4th aspect, it is preferable to contain at least a black color material from a light-shielding viewpoint, and it is more preferable to contain at least carbon black. In addition, from the viewpoint of easily suppressing the drop in the voltage holding ratio of the liquid crystal, suppressing the absorption of ultraviolet rays, and controlling the shape and the level difference, it is more preferable to include at least the above Described organic black pigment. From the viewpoint of light-shielding properties, and both the suppression of the reduction in the voltage holding ratio of the liquid crystal and the controllability of the shape or level difference, carbon black and an organic black pigment may be used in combination.

In the photosensitive coloring composition for coloring spacer formation of the 4th aspect, the preferable value in the photosensitive coloring composition of this invention mentioned below can be employ|adopted as a compounding quantity of these coloring agents. In addition, it may be appropriately adjusted according to the required optical density, and International Publication No. 2013/062011, International Publication No. 2013/115268, Japanese Patent Publication No. 2014-534460, and Japanese Patent Publication No. 2014-529652 may also be used. No., Japanese Patent Laid-Open No. 2014-146029, International Publication No. 2013/179237, Japanese Patent Laid-Open No. 2011-107707, and the like.

<(b) Alkali-soluble resin>,

The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth)acrylate-based resins, acrylic-based resins, and carboxyl group-containing resins. Epoxy resins, carboxyl group-containing urethane resins, novolak-based resins, polyvinylphenol-based resins, etc., among which epoxy (meth)acrylate-based resins and acrylic-based resins are preferred. These can be used individually by 1 type, or can be used by mixing a plurality of types.

As the (b) alkali-soluble resin used in the present invention, the following alkali-soluble resin (b1) and/or alkali-soluble resin (b2) can be preferably used in particular from the viewpoint of excellent plate-making properties (hereinafter, Sometimes referred to as "carboxy-containing epoxy (meth)acrylate resin").

<Alkali-soluble resin (b1)>

Alkali-soluble resin obtained by adding epoxy resin to α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having carboxyl group, and then reacting with polybasic acid and/or its acid anhydride .

<Alkali-soluble resin (b2)>

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

As the epoxy resin used as the raw material, for example, bisphenol A epoxy resin (for example, "Epikote (registered trademark, the same below) 828", "Epikote 1001", "Epikote 1002", "Epikote1004", etc.), epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol A epoxy resins with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323) manufactured by Nippon Kayaku Co., Ltd. , softening point 76°C)), bisphenol F type resin (for example, "Epikote807", "EP-4001", "EP-4002", "EP-4004" manufactured by Mitsubishi Chemical Corporation), by bisphenol F The epoxy resin obtained by the reaction of the alcoholic hydroxyl group of the epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent weight 350, softening point 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenolic novolak type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), (ortho, meta, para) cresol novolak epoxy resins (for example, Nippon Kayaku) "EOCN (registered trademark, the same below)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC ( registered trademark)”), trisphenolmethane type epoxy resin (for example, “EPPN (registered trademark, below) manufactured by Nippon Kayaku Co., Ltd. Same as)-501", "EPN-502", "EPPN-503"), alicyclic epoxy resin ("Celloxide2021P", "Celloxide (registered trademark, the same below) EHPE" manufactured by Daicel Chemical Industry Co., Ltd.), will be Epoxy resins obtained by glycidylation of a phenolic resin obtained by the reaction of dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Corporation), the following Epoxy resins etc. represented by the general formulae (B1) to (B4).

Specifically, as the epoxy resin represented by the following general formula (B1), "XD-1000" manufactured by Nippon Kayaku Co., Ltd. can be mentioned, and as the epoxy resin represented by the following general formula (B2), there can be mentioned "NC-3000" manufactured by Nippon Kayaku Co., Ltd., "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., etc., can be mentioned as the epoxy resin represented by the following general formula (B4).

[hua 6]

In the above general formula (B1), a represents an average value and represents a number of 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. In addition, several R ¹¹¹ existing in 1 molecule may be the same or different, respectively.

[hua 7]

In the above general formula (B2), b represents an average value and represents a number of 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. In addition, a plurality of R ¹²¹ present in one molecule may be the same or different, respectively.

[hua 8]

In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). Among them, one or more adamantane structures are included in the molecular structure. c represents an integer of 2 or 3.

[Chemical 9]

[Chemical 10]

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

[Chemical 11]

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

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

Examples of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, ortho-, meta- or para-vinyl benzoic acid, (meth)acrylic acid, α-haloalkyl, alkoxy, halogen, nitro, cyano substituents of acrylic acid, monocarboxylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(methyl) ) Acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-( Meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylsuccinic acid, 2-(meth)acryloyloxypropyladipic acid, 2-(methyl)acryloyloxypropylsuccinic acid ) acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxypropyl phthalic acid Meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-( Meth)acryloyloxybutylphthalic acid, 2-(meth)acryloyl Oxybutylmaleic acid, a single product obtained by adding (meth)acrylic acid to lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone (meth)acrylic acid hydroxyalkyl ester, pentaerythritol tri(meth)acrylate and acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride), etc. Monomers, (meth)acrylic acid dimers, etc. Among these, in terms of sensitivity, (meth)acrylic acid is particularly preferred.

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

As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, tetramethylammonium chloride, tetraethylammonium chloride, Quaternary ammonium salts such as dodecyl trimethyl ammonium chloride, etc.

Furthermore, an epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and an esterification catalyst may be used alone or in combination of two or more.

The use 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 relative to 1 equivalent of epoxy groups of the epoxy resin, and more Preferably, it is in the range of 0.7 to 1.1 equivalents.

If the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group is small, the amount of unsaturated group introduced is insufficient, and the subsequent interaction with polybasic acid and/or its anhydride The response also became insufficient. Moreover, it is also disadvantageous that a large amount of epoxy groups remain. On the other hand, when 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 to deteriorate the hardening characteristics was found.

Examples of the polybasic acid and/or its acid anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, partial Benzenetricarboxylic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloramphenicol, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid , and one or more of these acid anhydrides.

Preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or such anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

For the addition reaction of the polybasic acid and/or its acid anhydride, a known method can also be used, and it can be used in the reaction with epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group. Under the same conditions as the addition reaction, continue the reaction to obtain the target compound.

Regarding the addition amount of the polybasic acid and/or its acid anhydride component, 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 more preferably Preferably, it is 50 mgKOH/g or more. Moreover, it is preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, and still more preferably 120 mgKOH/g. By setting it as the said lower limit or more, there exists a tendency for alkali developability to become favorable, and it exists in the tendency for hardenability to become favorable by setting it as the said upper limit or less.

In addition, polyfunctional alcohols, such as trimethylolpropane, pentaerythritol, and dipentaerythritol, can also be added at the time of addition reaction of this polybasic acid and/or its acid anhydride, and a polybranched structure can also be introduce|transduced.

Carboxyl-containing epoxy (meth)acrylate resins are usually After mixing polybasic acid and/or its anhydride with the reactant of oxygen resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group, or after adding epoxy resin and α,β- The reactant of unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is obtained by mixing a polybasic acid and/or its anhydride and a polyfunctional alcohol, and then heating.

In this case, the mixing order of the polybasic acid and/or its acid anhydride and the polyfunctional alcohol is not particularly limited. By heating, polybasic acids and/or their anhydrides are used in the reaction of epoxy resins with α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with carboxyl groups and polyfunctional alcohols Any hydroxyl group in the mixture undergoes an addition reaction.

The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably It is 2000 or more, More preferably, it is 3000 or more, More preferably, it is 4000 or more. Moreover, it is 10000 or less normally, Preferably it is 8000 or less, More preferably, it is 6000 or less. If the weight average molecular weight is small, the solubility in the developing solution will be high, and if it is too large, the solubility in the developing solution will be low.

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

Moreover, a part of the said carboxyl group-containing epoxy (meth)acrylate resin can also 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, it is preferable to make the ratio of the epoxy (meth)acrylate resin containing a carboxyl group in (b) alkali-soluble resin 50 mass % or more, especially 80 mass % or more.

The other binder resin that can be used together with the carboxyl group-containing epoxy (meth)acrylate resin is not limited, as long as it is selected from resins generally used for photosensitive coloring compositions. For example, Japanese Patent Laid-Open No. 2007-271727, Japan Binder resins and the like described in Japanese Patent Laid-Open No. 2007-316620, Japanese Patent Laid-Open No. 2007-334290, and the like. In addition, any other binder resin may be used individually by 1 type, and may be used in combination of 2 or more types.

In addition, as the (b) alkali-soluble resin, an acrylic resin is preferably used from the viewpoint of compatibility with a pigment, a dispersant, etc., and the one described in Japanese Patent Laid-Open No. 2014-137466 can be preferably used .

Examples of the acrylic resin include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, referred to as "unsaturated monomer (b1)") and other copolymerizable ethylenically unsaturated monomers (hereinafter, referred to as "unsaturated monomer (b1)"). , referred to as "unsaturated monomer (b2)") copolymer.

Examples of the unsaturated monomer (b1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; such as maleic acid, maleic anhydride, and fumaric acid. , itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, unsaturated dicarboxylic acids of mesaconic acid or their anhydrides; succinic acid mono[2-(meth)acryloyloxyethyl]ester, Mono[(meth)acryloyloxyalkyl]ester of polycarboxylic acid with more than 2 valences of mono[2-(meth)acryloyloxyethyl]phthalate; such as ω-carboxypolyhexamethylene Lactone mono(meth)acrylate is a mono(meth)acrylate of a polymer having carboxyl groups and hydroxyl groups at both ends; p-vinyl benzoic acid, etc. These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

In addition, as the unsaturated monomer (b2), for example, N-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide; such as styrene, Aromatic vinyl compounds of α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, vinyl naphthalene;

酯、(甲基)丙烯酸三環[5.2.1.0^2,6]癸烷-8-酯、(甲基)丙烯酸二環戊烯酯、丙三醇單(甲基)丙烯酸酯、(甲基)丙烯酸4-羥基苯酯、對茴香基酚之環氧乙烷改質(甲基)丙烯酸酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸3,4-環氧環己基甲酯、3-[(甲基)丙烯醯氧基甲基]氧雜環丁烷、3-[(甲基)丙烯醯氧基甲基]-3-乙基氧雜環丁烷之(甲基)丙烯酸酯； Such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, Benzyl (meth)acrylate, polyethylene glycol (polymerization degree 2~10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2~10) methyl ether (meth)acrylate, polyethylene glycol (Polymerization degree 2~10) Mono(meth)acrylate, Polypropylene glycol (Polymerization degree 2~10) Mono(meth)acrylate, Cyclohexyl(meth)acrylate, (meth)acrylate iso

ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decane-8-ester, (meth)acrylate dicyclopentenyl, glycerol mono(meth)acrylate, (meth) 4-Hydroxyphenyl acrylate, ethylene oxide modified (meth)acrylate of p-anisylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate , 3-[(meth)acryloyloxymethyl]oxetane, (methyl) of 3-[(meth)acryloyloxymethyl]-3-ethyloxetane Acrylate;

基乙烯醚、三環[5.2.1.0^2,6]癸烷-8-基乙烯醚、五環十五烷基乙烯醚、3-(乙烯氧基甲基)-3-乙基氧雜環丁烷之乙烯醚；如聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷之於聚合體分子鏈之末端具有單(甲基)丙烯醯基之巨單體等。該等不飽和單體(b2)可單獨使用或者將2種以上混合而使用。 such as cyclohexyl vinyl ether, iso

vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane Vinyl ethers of alkanes; such as polystyrene, polymethyl (meth)acrylate, poly(n-butyl) (meth)acrylate, polysiloxane, which have a mono(meth)acryloyl group at the end of the polymer molecular chain The giant monomer, etc. These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

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, and more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) within such a range, there is a tendency that a photosensitive coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, and Japanese Patent Laid-Open No. 8-259876. Gazette No. 10-31308, Japan Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2004-101728, etc. revealed copolymers.

The copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) can be produced by a known method, for example, Japanese Patent Laid-Open No. 2003-222717 and Japanese Patent Laid-Open No. 2006-259680 , International Publication No. 2007/029871, etc. to control its structure or Mw, Mw/Mn.

<(c) Photopolymerization Initiator>

(c) The photopolymerization initiator is a component having the function of directly absorbing light and causing a decomposition reaction or a dehydrogenation reaction to generate a polymerization active radical. Additives, such as a polymerization accelerator (chain transfer agent) and a sensitizing dye, can also be added and used as needed.

The (c) photopolymerization initiator in the photosensitive coloring composition of the present invention contains an oxime ester-based compound represented by the following formula (I). As described above, it is considered that by including the oxime ester compound represented by the following formula (I), the light absorption to long-wavelength light is increased due to the naphthalene ring contained in the carbazole skeleton, and the crosslinking inside the coating film can be improved. In addition, since the structure has halogen atoms, the compound is easily distributed on the surface of the coating film, and the crosslinking density on the surface of the film can be suppressed from being excessively high due to the influence of oxygen barrier.

[Chemical 12]

In the above general formula (I),

R ¹ represents an aromatic ring group which may have a substituent.

R ² represents an optionally substituted alkane group or an optionally substituted aryl group.

R ³ represents a hydrogen atom or an alkyl group which may have a substituent.

R ⁴ represents an aromatic ring group which may have a substituent.

R ⁵ and R ⁶ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. Wherein, at least one of R ⁵ and R ⁶ is a naphthalene ring which may have a substituent.

At least any one of R ¹ and R ⁴ has a -OR ⁷ group as a substituent. wherein R ⁷ represents a haloalkyl group.

X represents a direct bond or a carbonyl group.

Z represents a direct bond or a carbonyl group.

As an aromatic ring group in R< ¹ >, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, and still more preferably 8 or less. Moreover, it is 4 or more normally, Preferably it is 6 or more. By setting it as the said upper limit or less, there exists a tendency for solubility to become favorable, and by setting it as more than the said lower limit, it exists in the tendency for both sensitivity and solubility to be easily compatible.

環、聯三伸苯環、乙烷合萘環、熒蒽環、茀環等。 The 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 single ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, a benzene ring, and a benzene ring. and pyrene ring,

ring, bi-triphenylene ring, ethanenaphthalene ring, fluoranthene ring, perylene ring, etc.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異 噻唑環、苯并咪唑環、吡啶環、吡

環、嗒

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等。 In addition, the aromatic heterocyclic group means an aromatic heterocyclic ring having one free valence. The aromatic heterocyclic ring of the aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring. ring,

oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thieno furan ring, benziso

azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine

ring, click

ring, pyrimidine ring, three

ring, quinoline ring, isoquinoline ring,

quinoline, quinoline

Linen ring, phenanthrene ring, benzimidazole ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

Examples of the substituent which the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a haloalkyl group (an alkyl group in which a part or all of a hydrogen atom is substituted with a halogen atom), a haloalkoxy group From the viewpoint of surface hardening properties, such as an alkoxy group in which a part or all of a hydrogen atom is substituted with a halogen atom, a halogen atom, a haloalkyl group, or a haloalkoxy group is preferable, and further, from the viewpoint of ease of synthesis From a viewpoint, it is preferable not to be substituted.

Among these, from the viewpoint of sensitivity, an aromatic hydrocarbon ring group which may have a substituent is preferable, and a phenyl ring group which may have a substituent is more preferable.

The carbon number of the alkanoyl group in R ² is not particularly limited, but from the viewpoint of sensitivity, it is preferably 2 or more. Moreover, from a viewpoint of sensitivity, 20 or less are preferable, 12 or less are more preferable, 7 or less are still more preferable, 5 or less are still more preferable, 3 or less are especially preferable.

Specific examples of the alkanoyl group include an acetyl group, a propionyl group, a butyryl group, and the like. Among these, an acetyl group or a propionyl group is preferred, and an acetyl group is more preferred from the viewpoint of sensitivity. . As a substituent which an alkanoyl group may have, a hydroxyl group, an alkoxy group, a halogen atom, etc. are mentioned, and it is preferable that it is not substituted from the viewpoint of sensitivity.

The carbon number of the aryl group in R ² is not particularly limited, but from the viewpoint of sensitivity, it is preferably 7 or more. Moreover, from a viewpoint of sensitivity, 20 or less are preferable, 12 or less are more preferable, 10 or less are still more preferable, and 8 or less are especially preferable.

Specific examples of the aryl group include a benzyl group, a methyl benzyl group, a naphthyl group, and the like, and among these, a benzyl group is more preferred from the viewpoint of sensitivity.

Examples of the substituent which the aryl aryl group may have include a hydroxyl group, an alkoxy group, a halogen atom, and the like, and from the viewpoint of sensitivity, it is preferably unsubstituted. Among these, from the viewpoint of sensitivity, R ² is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and more preferably an acetyl group base.

The number of carbon atoms of the alkyl group in R ³ is not particularly limited, but from the viewpoint of solubility, preferably 1 or more, more preferably 2 or more, still more preferably 5 or more, particularly preferably 7 or more. Moreover, from the viewpoint of compatibility, 20 or less are preferable, 15 or less are more preferable, and 10 or less are still more preferable.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, and the like, among these, from the viewpoint of solubility Specifically, an octyl group or a 2-ethylhexyl group is preferable, and a 2-ethylhexyl group is more preferable.

Examples of the substituent which 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 alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably 2-ethyl base hex.

As an aromatic ring group in R< ⁴ >, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, and still more preferably 8 or less. Moreover, it is 4 or more normally, Preferably it is 6 or more. By setting it as the said upper limit or less, there exists a tendency for solubility to become favorable, and by setting it as more than the said lower limit, it exists in the tendency for both sensitivity and solubility to be easily compatible.

環、聯三伸苯環、乙烷合萘環、熒蒽環、茀環等。 The 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 single ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, a benzene ring, and a benzene ring. and pyrene ring,

ring, bi-triphenylene ring, ethanenaphthalene ring, fluoranthene ring, perylene ring, etc.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、嗒

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等。 In addition, the aromatic heterocyclic group means an aromatic heterocyclic ring having one free valence. The aromatic heterocyclic ring of the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. 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, furanofuran ring, thieno furan ring, benziso

azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine

ring, click

ring, pyrimidine ring, three

ring, quinoline ring, isoquinoline ring,

quinoline, quinoline

Linen ring, phenanthrene ring, benzimidazole ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

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

The number of substituents is not particularly limited, but from the viewpoint of solubility, preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. Moreover, from the viewpoint of compatibility, 10 or less are preferable, 5 or less are more preferable, and 4 or less are still more preferable.

Among these, from the viewpoint of solubility, R ⁴ is preferably an aromatic hydrocarbon ring group which may have a substituent, more preferably an aromatic hydrocarbon ring group having two or more methyl groups , and more preferably 2,4,6-trimethylphenyl.

R ⁵ and R ⁶ each independently represent a benzene ring or a naphthalene ring which may have a substituent. Wherein, at least one of R ⁵ and R ⁶ is a naphthalene ring which may have a substituent. As a specific combination, it can be enumerated: R ⁵ is a combination of a benzene ring which may have a substituent and R ⁶ is a combination of a naphthalene ring which may have a substituent, R ⁵ is a naphthalene ring which may have a substituent, and R ⁶ is a naphthalene ring which may have a substituent A combination of benzene rings, R ⁵ is a naphthalene ring which may have a substituent, and R ⁶ is a combination of a naphthalene ring which may have a substituent.

Among these, from the viewpoint of light absorption, R ⁵ is a combination of a naphthalene ring which may have a substituent and R ⁶ is a benzene ring which may have a substituent.

When R ⁵ is a benzene ring which may have a substituent, an N atom is bonded to the 1-position of the benzene ring, R ⁶ is bonded to the 2-position, and an X is bonded to the 4-position. Similarly, when R ⁶ is a benzene ring which may have a substituent, 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.

On the other hand, when R ⁵ is a naphthalene ring which may have a substituent, X, N atom and R ⁶ bonded to R ⁵ in formula (I) may also be bonded to any position of the naphthalene ring. 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, or R 6 is bonded to the 1-position of the naphthalene ring, and R ⁶ is bonded to the 2-position An aspect in which an N atom is bonded to the 6-position and an X is bonded to the 6-position, and the like.

Similarly, when R ⁶ is a naphthalene ring which may have a substituent, the Z, N atom and R ⁵ bonded to R ⁶ in formula (I) may also be bonded to any position of the naphthalene ring. 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; or R ⁵ is bonded to the 1-position of the naphthalene ring; There is an N atom bonded to the 6-position, and Z is bonded to the 6-position.

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

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

R ⁷ represents a haloalkyl group, and the number of carbon atoms in the haloalkyl group in R ⁷ is not particularly limited, but from the viewpoint of solubility, preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. Moreover, from the viewpoint of compatibility, 10 or less are preferable, 7 or less are more preferable, and 5 or less are still more preferable. The carbon chain in the haloalkyl group may be straight chain, branched chain, or cyclic, but from the viewpoint of ease of production, straight chain is preferred.

The number of halogen atoms in the haloalkyl group is not particularly limited, but from the viewpoint of solubility, preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. Moreover, from the viewpoint of compatibility, it is preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less.

Specific examples of the haloalkyl group include 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoroethyl, 2,2,3,3,4,4,5,5 -Octafluoropentyl and the like, among these, 2,2,3,3-tetrafluoropropyl is more preferred from the viewpoint of ease of production. As a substituent which a haloalkyl group may have, a hydroxyl group, an alkoxy group, etc. are mentioned, From a viewpoint of easiness of manufacture, unsubstituted is preferable.

X represents a direct bond or a carbonyl group, a direct bond is preferable from the viewpoint of adhesiveness, and a carbonyl group is preferable from the viewpoint of sensitivity. Moreover, Z represents a direct bond or a carbonyl group, and a direct bond is preferable from the viewpoint of adhesiveness, and a carbonyl group is preferable from the viewpoint of sensitivity.

As a specific example of the oxime ester type compound represented by the said general formula (I), the following are mentioned.

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[hua 20]

The (c) photopolymerization initiator in the photosensitive coloring composition of the present invention includes the oxime ester compound represented by the above-mentioned general formula (I), and may further include another photopolymerization initiator.

二唑衍生物、鹵甲基-對稱三

衍生物、N-苯基甘胺酸等N-芳基-α-胺基酸類、N-芳基-α-胺基酸鹽類、N-芳基-α-胺基酸酯類等自由基活性劑、α-胺烷基苯酮衍生物；日本專利特開2000-80068號公報、日本專利特開2006-36750號公報、國際公開第2008/075564號、國際公開第2009/131189號等所記載之肟酯衍生物等。 As other photopolymerization initiators, for example, there may be mentioned: dimetallocene compounds containing titanocene compounds described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Japanese Patent Laid-Open No. 61-151197 Hexaarylbiimidazole derivatives described in Kokai No. 2000-56118; Halomethylation described in Japanese Patent Laid-Open No. 10-39503

oxadiazole derivatives, halomethyl-symmetric three

Derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other radicals Active agents, α-aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, International Publication No. 2008/075564, International Publication No. 2009/131189, etc. The described oxime ester derivatives, etc.

A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types. Among the photopolymerization initiators, sensitizing dyes and polymerization accelerators corresponding to the wavelength of the image exposure light source can be prepared as needed to improve the sensitivity. Examples of sensitizing dyes include: Japanese Patent Laid-Open No. Hei 4-221958, dibenzopyran dyes described in Japanese Patent Laid-Open No. Hei 4-219756, Japanese Patent Laid-Open No. Hei 3-239703, Japanese Patent Laid-Open No. 3-239703 Coumarin pigments with heterocycles described in Kokai Hei 5-289335, 3-ketocoumarin compounds described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, Japanese Patent Pyrromethylene dyes described in Japanese Patent Laid-Open No. 6-19240, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 47-2528 Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-59- Japanese Patent Laid-Open No. 56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. Sho 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, Japanese Patent Laid-Open No. 5-107761 The dye etc. which have a dialkylaminobenzene skeleton are described in Unexamined-Japanese-Patent No. 4-288818.

唑、2-(對二乙胺基苯基)苯并

唑、2-(對二甲胺基苯基)苯并[4,5]苯并

唑、2-(對二甲胺基苯基)苯并[6,7]苯并

唑、2,5-雙(對二乙胺基苯基)-1,3,4-

唑、2-(對二甲胺基苯基)苯并噻唑、2-(對二乙胺基苯基)苯并噻唑、2-(對二甲胺基苯基)苯并咪唑、2-(對二乙胺基苯基)苯并咪唑、2,5-雙(對二乙胺基苯基)-1,3,4-噻二唑、(對二甲胺基苯基)吡啶、(對二乙胺基苯基)吡啶、(對二甲胺基苯基)喹啉、(對二乙胺基苯基)喹啉、(對二甲胺基苯基)嘧啶、(對二乙胺基苯基)嘧啶等含對二烷胺基苯基之化合物等。其中最佳者為4,4'-二烷胺基苯并苯酮。又，增感色素可單獨使用1種，亦可併用2種以上。 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-aminodiphenyl Benzophenone compounds such as ketone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl)benzo

azole, 2-(p-diethylaminophenyl)benzo

azole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo

azole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo

azole, 2,5-bis(p-diethylaminophenyl)-1,3,4-

azole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-dimethylaminophenyl)benzimidazole p-Diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-Diethylaminophenyl) Diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl) Phenyl) pyrimidine and other compounds containing p-dialkylamino phenyl, etc. The best among them is 4,4'-dialkylaminobenzophenone. Moreover, a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

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

<(d) Ethylenically unsaturated compound>

The photosensitive coloring composition of this invention contains (d) an ethylenically unsaturated compound. The sensitivity is improved by including (d) an ethylenically unsaturated compound. Vinyl used in the present invention An unsaturated compound is a compound which has at least 1 ethylenically unsaturated group in a molecule|numerator. Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, and a monoester of a carboxylic acid having one ethylenically unsaturated bond and a polyvalent or monovalent alcohol can be mentioned. Wait.

In this invention, it is especially preferable to use the polyfunctional vinylic monomer which has two or more ethylenically unsaturated groups in 1 molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less. By making it more than the said lower limit value, there exists a tendency for high sensitivity, and there exists a tendency for the solubility to a solvent to improve by making it into the said upper limit value or less.

Examples of polyfunctional vinyl monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds Polyvalent hydroxy compounds such as hydroxy compounds, and esters obtained by esterification with unsaturated carboxylic acids and polyvalent carboxylic acids, and the like.

Examples of esters of the aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates of aliphatic polyhydroxy compounds such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. The acrylates of these exemplified compounds are replaced by methacrylates of methacrylates, itaconate by itaconates, crotonates by crotonates, or maleate by maleate Maleic acid esters, etc.

As the ester of aromatic polyhydroxy compound and unsaturated carboxylic acid, it can be listed Examples: aromatic polyhydroxyl groups such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, etc. Compounds of acrylate and methacrylate, etc.

The ester obtained by the esterification reaction of a polyvalent carboxylic acid, an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single product, but representative specific examples include: acrylic acid, phthalic acid, and ethylene glycol The condensate of acrylic acid, maleic acid and diethylene glycol; the condensate of methacrylic acid, terephthalic acid and pentaerythritol; the condensate of acrylic acid, adipic acid, butanediol and glycerol, etc.

In addition, as an example of the polyfunctional vinylic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl-containing (meth)acrylate, or a polyisocyanate compound and a polyol and a hydroxyl-containing (meth)acrylate are used. Urethane (meth)acrylate obtained by acrylate reaction; such as epoxy acrylates of addition reactants of polyvalent epoxy compounds and hydroxyl (meth)acrylate or (meth)acrylic acid; extension Acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are useful.

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

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

<(e) Solvent>

The photosensitive coloring composition of this invention contains (e) a solvent. By including the (e) solvent, the pigment can be dispersed in the solvent, and coating becomes easy. The photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and if necessary Various other materials used are used in a state of being dissolved or dispersed in a solvent. Among the solvents, from the viewpoint of dispersibility and coatability, organic solvents are preferred.

Among the organic solvents, from the viewpoint of coatability, it is preferable to select a boiling point in a range of 100 to 300°C, and more preferably a boiling point in a range of 120 to 280°C. In addition, the so-called boiling point here means the boiling point under a pressure of 1013.25 hPa.

As such an organic solvent, the following are mentioned, for example. Such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tertiary butyl ether, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl amyl alcohol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-ethyl Glycol monoalkyl ethers of oxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

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 Glycol dialkyl ethers;

Such as 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, Ethylene Glycol 3-methoxybutyl acid, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate Propylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ethers of 3-methyl-3-methoxybutyl acetate acetates;

Glycol diacetate such as ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

Such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isoacetone, methyl isoamyl ketone, diisoacetone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl Ketones of methylbutanone, methylhexanone, methylnonanone, methoxymethylpentanone;

Such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentanol, glycerol, benzyl Monohydric or polyhydric alcohols of base alcohols;

Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutene, n-hexane, hexene, isoprene, dipentene, dodecane; such as cyclohexane, methylcyclohexane, methylcyclohexane Alicyclic hydrocarbons of hexene and bicyclohexane;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol Alcohol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethyl acetate Methyl oxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, 3-methylpropionate Chain or cyclic esters of butyl oxypropionate and γ-butyrolactone;

Such as alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; such as Nitriles of acetonitrile, benzonitrile, etc.

Examples of commercially available organic solvents that meet the above include: mineral spirits, Varsol#2, Apco#18 solvent, Apco thinner, Socal Solvent No.1 and No.2, Solvesso#150, Shell TS28 Solvent, Carbide Alcohol, ethyl carbitol, butyl carbitol, Methyl Cellosolve ("Cellosolve" is a registered trademark, the same below), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (all are trade names), etc. These organic solvents may be used alone or in combination of two or more.

In the case of forming the colored spacer by photolithography, as the organic solvent, it is preferable to select the one whose boiling point is in the range of 100 to 200° C. (under a pressure of 1013.25 hPa. Hereinafter, the boiling point is all the same). More preferably, it has a boiling point of 120-170 degreeC.

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability and surface tension, and relatively high solubility of constituent components in the composition. In addition, the glycol alkyl ether acetates may be used alone, or other organic solvents may be used in combination. As an organic solvent used together, glycol monoalkyl ethers are especially preferable.

Among them, propylene glycol monomethyl ether is particularly preferred in terms of solubility of the constituents in the composition. Furthermore, glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to agglomerate, and the viscosity of the coloring resin composition obtained thereafter tends to decrease in storage stability. The ratio of glycol monoalkyl ethers is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

In addition, an organic solvent having a boiling point of 150°C or higher (the following may be used in combination) The case referred to as "high boiling point solvent") is also preferred. By using such a high boiling point solvent in combination, the photosensitive coloring composition is not easily dried, and the uniform dispersion state of the pigment in the composition is prevented from being destroyed by rapid drying.

That is, for example, there is an effect of preventing foreign matter defects caused by precipitation and curing of color materials and the like at the tip of the slit nozzle. In terms of the high effect, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable.

The content ratio of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting the above lower limit value or more, for example, it is possible to suppress the tendency of color materials, etc. to precipitate and solidify at the front end of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the composition can be suppressed. The drying temperature becomes slower, which can suppress the tendency of poor rhythm in the decompression drying step or the porosity of pre-baking.

Furthermore, the high-boiling solvent with a boiling point of 150°C or higher may be glycol alkyl ether acetates, or may be glycol alkyl ethers, and in this case, it may not contain a high-boiling solvent with a boiling point of 150°C or higher. solvent.

As a preferable high boiling point solvent, for example, among the above-mentioned various solvents, 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, triacetin, etc.

<(f) Dispersant>

In the photosensitive coloring composition of the present invention, finely dispersing the colorant (a) and stabilizing the dispersion state are important to ensure the stability of quality, so (f) is included. Dispersant.

等來自含氮雜環之基等官能基的高分子分散劑。 The (f) dispersant is preferably a polymer dispersant having a functional group, and further, in terms of dispersion stability, preferably has a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a salt group of these; Primary, secondary or tertiary amine group; quaternary ammonium base; pyridine, pyrimidine, pyridine

It is a polymer dispersant derived from functional groups such as nitrogen-containing heterocyclic groups.

等來自含氮雜環之基等鹼性官能基之高分子分散劑，就將顏料分散時能以少量分散劑進行分散之觀點而言尤佳。 Among them, especially with primary, secondary or tertiary amine group; quaternary ammonium salt group; pyridine, pyrimidine, pyridine

A polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group is particularly preferred from the viewpoint of dispersing the pigment with a small amount of the dispersant.

Moreover, as a polymer dispersant, for example, a urethane-based dispersant, an acrylic-based dispersant, a polyethylenimine-based dispersant, a polyallylamine-based dispersant, and a monomer containing an amine group can be mentioned. And macromonomer dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants , Aliphatic modified polyester dispersant, etc.

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

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

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

As a urethane-based polymer dispersant, if a preferable chemical structure is specifically exemplified, for example, a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule can be mentioned. A dispersion resin with a weight average molecular weight of 1,000 to 200,000 obtained by reacting with a compound having active hydrogen and a tertiary amine group in the same molecule. By treating these with a quaternary agent such as benzyl chloride, all or a part of the tertiary amine groups can be turned into quaternary ammonium salt groups.

Examples of the above-mentioned polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate Aromatic diisocyanates such as isocyanates, toluidine diisocyanate, hexamethylene diisocyanate, methyl lysine diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), ω,ω'-diisocyanatodimethylcyclohexane and other alicyclic diisocyanates, benzene diisocyanate Aliphatic diisocyanates with aromatic rings such as methyl diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, lysinate triisocyanate, 1,6,11-undecane Triisocyanate, 1,8- Diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatobenzene thiophosphate) triisocyanates such as base) esters, and these trimers, water adducts, and these polyol adducts, etc.

The preferred polyisocyanates are trimers of organic diisocyanates, and the most preferred ones are trimers of toluene 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 isocyanates, there may be mentioned a method in which an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, and carboxylates is used for the above-mentioned polyisocyanates The partial trimerization of isocyanate groups is carried out by the addition of catalyst poisons, and after the trimerization is stopped by the addition of catalyst poisons, the unreacted polyisocyanates are subjected to solvent extraction and removed by thin-film distillation to obtain the target isocyanide-containing Urate-based polyisocyanates.

Examples of compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether diols, polyester diols, polycarbonate diols, polyolefin diols, and the like, and these compounds The single-terminal hydroxyl group is an alkyl group having 1 to 25 carbon atoms and is alkoxylated and a mixture of two or more of these.

Examples of the polyether diol include polyether diol, polyether ester diol, and a mixture of two or more of these. As the polyether glycol, one obtained by homopolymerizing or copolymerizing an alkylene oxide, for example, polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer, polyoxytetramethylene glycol, polyoxyhexamethylene glycol can be mentioned. Methylene glycol, polyoxyoctamethylene glycol, and a mixture of two or more of them.

Examples of the polyetheresterdiol include a dicarboxylic acid or an acid anhydride thereof by reacting an ether group-containing diol or a mixture with other diols, or a polyesterdiol What is obtained by reacting with an alkylene oxide, for example, poly (polyoxytetramethylene) adipate etc. are mentioned.

The best polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which the single-terminal hydroxyl group of these compounds is an alkyl group with 1 to 25 carbon atoms and is alkoxylated .

Examples of polyester diols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or acid anhydrides thereof and the like Alcohols (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 diols, 2-methyl-1,8-octamethylene glycol, aliphatic diols such as 1,9-nonanediol, alicyclic diols such as bishydroxymethylcyclohexane, phthalodiol Polyethylene glycol, aromatic diols such as bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.) obtained by polycondensation, such as polyethylene adipate, polyethylene adipate, etc. Butylene diacid, polyhexamethylene adipate, polyethylene/propylene adipate, etc., or polymers obtained by using the above-mentioned diols or monohydric alcohols with 1 to 25 carbon atoms as initiators Lactone diol or polylactone monool, such as polycaprolactone diol, polymethylvalerolactone, and mixtures of two or more of these. As the polyester diol, polycaprolactone diol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator is most preferable.

As the polycarbonate diol, poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-amylene) carbonate, etc. are mentioned, and as the polyolefin diol, polybutylene is mentioned. Diene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, etc. These may be used individually by 1 type, and may use 2 or more types together.

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

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

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

Examples of such compounds having active hydrogen and a tertiary amine group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3- Propylene diamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N -Diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N- Diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc.

唑環、苯并噻唑環、苯并噻二唑環等含氮雜五元環、吡啶環、嗒

環、嘧啶環、三

環、喹啉環、吖啶環、異喹啉環等含氮雜六元環。該等含氮雜環中，較佳者為咪唑環或三唑環。 In addition, as the nitrogen-containing heterocyclic ring when the tertiary amino group is a nitrogen-containing heterocyclic ring structure, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indole ring can be mentioned. azole ring, benzimidazole ring, benzotriazole ring, benzo

azole ring, benzothiazole ring, benzothiadiazole ring and other nitrogen-containing hetero five-membered rings, pyridine ring, pyridine ring

ring, pyrimidine ring, three

Ring, quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing hetero six-membered rings. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferable.

Specific examples of compounds having these imidazole rings and amino groups include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl) Imidazole etc.

Moreover, if the compound which has a triazole ring and an amino group is specifically illustrated, 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3 -Phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H- 1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, etc. .

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

The preferred mixing ratio of raw materials for the production of urethane-based polymer dispersants is 10 compounds with a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule relative to 100 parts by mass of the polyisocyanate compound. ~200 parts by mass, preferably 20-190 parts by mass, more preferably 30-180 parts by mass, the compound having active hydrogen and tertiary amine group in the same molecule is 0.2-25 parts by mass, preferably 0.3-24 parts by mass parts by mass.

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

In the above-mentioned production, a urethane reaction catalyst is usually used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate, and iron-based catalysts such as ferric acetonate and ferric chloride. Tertiary amines such as triethylamine and triethylenediamine, etc. These may be used individually by 1 type, and may use 2 or more types together.

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

Furthermore, in the case where the isocyanate group remains in the polymer dispersant in the above reaction, if the isocyanate group is further eliminated by an alcohol or an amine compound, the temporal stability of the product becomes high, which is preferable. The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and when it exceeds 200,000, the solubility is lowered, the dispersibility is poor, and it is difficult to control the reaction.

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

Examples of the unsaturated group-containing monomer having a functional group include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, and 2-(meth)acryloyloxyethylphthalate. Unsaturated monomers with carboxyl groups such as dicarboxylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, acrylic dimer, dimethylaminoethyl (meth)acrylate, (methyl) ) An unsaturated monomer having a tertiary amine group and a quaternary ammonium salt group, such as diethylaminoethyl acrylate and these quaternary products, is given as a specific example. These may be used individually by 1 type, and may use 2 or more types together.

酯、三環癸烷(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、N-乙烯基吡咯啶酮、苯乙烯及其衍生物、α-甲基苯乙烯、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-苄基馬來醯亞胺等N-取代馬來醯亞胺、丙烯腈、乙酸乙烯酯及聚(甲基)丙烯酸甲酯巨單體、聚苯乙烯巨單體、聚(甲基)丙烯酸2-羥基乙酯巨單體、聚乙二醇巨單體、聚丙二醇巨單體、聚己內酯巨單體等巨單體等。該等可單獨使用1種，亦可併用2種以上。 Examples of the unsaturated group-containing monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopropyl (meth)acrylate

Esters, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, alpha-methylstyrene, N-cyclohexymethylene N-substituted maleimide such as lyimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and poly(meth)acrylate Monomer, polystyrene macromonomer, poly(meth)acrylate 2-hydroxyethyl ester macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer and other macromonomers Wait. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer comprising an A block with a functional group and a B block without a functional group. In this case, the A block is derived from the above-mentioned functional group containing In addition to the partial structure of the unsaturated group-containing monomer, the partial structure of the above-mentioned non-functional group-containing unsaturated group-containing monomer can also be included, which can also be either random copolymerization or block copolymerization. contained in the A block. Moreover, content in the A block of the partial structure which does not contain a functional group is 80 mass % or less normally, Preferably it is 50 mass % or less, More preferably, it is 30 mass % or less.

The B block contains a partial structure derived from an unsaturated group-containing monomer that does not contain the above-mentioned functional group, and one B block may contain two or more types of monomer-derived monomers. Part of the structure, these can also be contained in the B block in either form of random copolymerization or block copolymerization.

The A-B or B-A-B block copolymer is prepared, for example, by the living polymerization method shown below. The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Among them, the polymerization active material of the anionic living polymerization method is an anion, and this method is represented by the following scheme, for example.

[Chemical 21]

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

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

[Chemical 22]

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

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

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

Furthermore, such block copolymers usually contain amine groups generated during the production process, and the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more. , more preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, and still more preferably 75 mgKOH/g or less.

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

Amine value [mgKOH/g]=(561×V)/(W×S)

[Wherein, W represents the weighed amount of the dispersant sample [g], V represents the titration amount [mL] at the end point of the titration, and S represents the solid content concentration of the dispersant sample [mass %]].

In addition, the amine value of the block copolymer also depends on the presence or absence and type of the acid group that is the basis of the acid value, but generally the lower one is better, usually below 10 mgKOH/g, and its weight average molecular weight (Mw) is higher than The range of 1000~100,000 is preferable. By setting it in the said range, there exists a tendency for favorable dispersibility to be ensured.

In the case of having a quaternary ammonium salt group as a functional group, the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferable to have a repeating unit represented by the following formula (i) (Hereinafter, it may be referred to as "repeating unit (i)").

[Chemical 23]

In the above formula (i), R ³¹ ～R ³³ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent, and R ³¹ ～R ³³ Two or more of them may be bonded to each other to form a ring structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group, and Y ^- is a counter anion.

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

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, Pentyl, hexyl, heptyl, octyl, etc., among them, preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, any of a linear form and a branched form may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

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

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

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

Specific examples of the aralkyl group include phenylmethylene, phenylethylidene, phenylpropylidene, phenylbutylene, phenylisopropylidene, and the like, and among them, phenylidene is preferred. Methylidene, phenylethylidene, phenylbutylene, or phenylbutylene, more preferably phenylmethylene, or phenylethylidene.

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

Moreover, in the case where the above-mentioned polymer dispersant has a tertiary amine as a functional group, it is preferable to have a repeating monomer represented by the following formula (ii) from the viewpoint of dispersibility bit (hereinafter, sometimes referred to as "repetition unit (ii)").

[Chemical 24]

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, R ³⁵ and R ³⁶ It is also possible to form a ring structure by bonding with each other. R ³⁷ is a hydrogen atom or a methyl group. Z is a bivalent linking group.

Moreover, as the alkyl group which may have a substituent among R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably used. Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably used. Further, as the optionally substituted aralkyl group in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably used.

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

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

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, -CONH-R ⁴³ -base, -COOR ⁴⁴ -base [wherein, R ⁴³ and R ⁴⁴ are single bonds, alkylene groups with 1 to 10 carbon atoms, or ether groups (alkoxyalkyl groups) with 2 to 10 carbon atoms], etc., Preferred is a -COO-R ⁴⁴ - group. Moreover, in said _formula (i), ^Cl- , _Br- ^, I- ^, ClO4-, ^{BF4- ,} _CH3COO- ^{, PF6-} etc. are mentioned as Y- ^of a counter anion _.

The content ratio of the repeating unit represented by the above formula (i) is not particularly limited. From the viewpoint of dispersibility, the total of the content ratio of the repeating unit represented by the above formula (i) and the content ratio of the repeating unit represented by the above formula (ii) is preferably 60 mol% or less, more preferably It is 50 mol% or less, more preferably 40 mol% or less, 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, particularly preferably 30 mol% or more.

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

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

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

[Chemical 25]

In the above formula (iii), R ⁴⁰ is an ethylidene or propylidene group, R ⁴¹ is an alkyl group which may have a substituent, and R ⁴² is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

The carbon number of the optionally substituted alkyl group in R ⁴¹ of the above formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more. Moreover, 10 or less are preferable, and 6 or less are more preferable.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. 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. Moreover, any of a linear form and a branched form may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

Moreover, 1 or more is preferable, and 2 or more is more preferable from the viewpoint of compatibility and dispersibility with respect to binder components, such as a solvent, with respect to n in the said formula (iii). Moreover, 10 or less are preferable, and 5 or less are more preferable.

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

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

[Chemical 26]

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

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

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. 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. Moreover, any of a linear form and a branched form may be sufficient. Moreover, cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

The carbon number of the optionally substituted aryl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 6 or more. Moreover, 16 or less are preferable, 12 or less are more preferable, and 8 or less are still more preferable.

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

The carbon number of the optionally substituted aralkyl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, and still more preferably 10 the following.

Specific examples of the aralkyl group include phenylmethylene, phenylethylidene, phenylpropylidene, phenylbutylene, phenylisopropylidene, and the like, and among them, phenylidene is preferred. Methylidene, phenylethylidene, phenylbutylene, or phenylbutylene, more preferably phenylmethylene, or phenylethylidene.

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

As a substituent which the alkyl group in ^R38 may have, a halogen atom, an alkoxy group, etc. are mentioned. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. In addition, the linear alkyl group represented by R ³⁸ also includes either a straight chain or a branched chain.

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

啉等單體之重複單位。 The polymer dispersant may also 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)acryloyl chloride; (meth)propylene (Meth) acrylamide monomers such as amide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N- methacrylate

Repeating units of monomers such as phenoline.

From the viewpoint of further improving the dispersibility, the polymer dispersant preferably contains an A block having the repeating unit (i) and the repeating unit (ii), and a block having no repeating unit (ii). A block copolymer having repeating units (i) and B blocks of repeating units (ii).

The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing not only a quaternary ammonium salt group but also a tertiary amine group into the A block, the dispersing ability of the dispersant unexpectedly tends to be significantly improved. Moreover, it is preferable that the B block has a repeating unit (iii), and it is more preferable that it has a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) can also be contained in any aspect of random copolymerization and block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may each contain two or more types in one A block, and in this case, random copolymerization or block copolymerization is also possible in the A block. Any aspect of the polymerization contains each repeating unit.

In addition, repeating units other than repeating unit (i) and repeating unit (ii) may be contained in the A block, and examples of such repeating units include repeating units derived from the above-mentioned (meth)acrylate-based monomers. units, etc. The content of repeating units other than repeating unit (i) and repeating unit (ii) in the A block is preferably 0-50 mol %, more preferably 0-20 mol %, and most preferably in the A block This repeating unit is not included.

啉等單體之重複單位。 Repeating units other than repeating units (iii) and (iv) may also be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; ( (Meth)acrylate-based monomers such as meth)acryloyl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylol acrylamide; vinyl acetate; propylene Nitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloyl

Repeating units of monomers such as phenoline.

The content of repeating units other than repeating unit (iii) and repeating unit (iv) in the B block is preferably 0-50 mol %, more preferably 0-20 mol %, and most preferably in the B block Such repeating units are not included.

In addition, from the viewpoint of improving dispersion stability, (f) the dispersant is preferably Used in combination with the following pigment derivatives.

<Other preparation components of the photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, in addition to the above-mentioned components, adhesion improvers such as silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, and pigment derivatives can be appropriately formulated things etc.

(1) Adhesion improver

In the photosensitive coloring composition of this invention, in order to improve the adhesiveness with a board|substrate, you may contain an adhesion improvement agent. As an adhesion improving agent, a silane coupling agent, a phosphoric acid group-containing compound, etc. are preferable. As a kind of a silane coupling agent, various silane coupling agents, such as an epoxy type, (meth)acrylic type, and an amine type, can be used individually by 1 type, or 2 or more types can be mixed and used.

As a preferable silane coupling agent, for example, (meth)acrylonitrile such as 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, etc. can be mentioned. Oxysilanes, 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldi Ethoxysilane, epoxysilanes such as 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethyl Isocyanatosilanes such as oxysilanes are particularly preferred as silane coupling agents such as epoxysilanes. The phosphoric acid group-containing compound is preferably a (meth)acryloyl group-containing phosphoric acid ester, and is preferably represented by the following general formula (g1), (g2) or (g3).

[Chemical 27]

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

(2) Surfactant

In the photosensitive coloring composition of this invention, in order to improve coatability, you may contain a surfactant.

As the surfactant, for example, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, it is preferable to use a nonionic surfactant because the possibility of adversely affecting each characteristic is low, and among them, a fluorine-based or silicon-based surfactant is more effective in coating properties.

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 Silicones Corporation), F-470, F-475, F-478, F-559 (DIC Corporation), SH7PA (Toray Silicone Corporation), DS-401 (Daikin Corporation), L-77 ( Nippon Unicar Co., Ltd.), FC4430 (Sumitomo 3M Co., Ltd.), etc. In addition, one type of surfactant may be used, or two or more types may be used in any combination and ratio. use together.

(3) Pigment derivatives

系、蒽醌系、陰丹士林系、苝系、紫環酮系、二酮基吡咯并吡咯系、二

系等衍生物，其中，較佳為酞菁系、喹酞酮系。 In the photosensitive coloring composition of the present invention, a pigment derivative may be contained as a dispersing aid in order to improve dispersibility and storage stability. As pigment derivatives, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, di

series, anthraquinone series, indanthrene series, perylene series, perylene series, diketopyrrolopyrrole series, diketopyrrolopyrrole series

Among them, phthalocyanine-based and quinophthalone-based derivatives are preferred.

The substituents of the pigment derivatives include sulfonic acid groups, sulfonamido groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like. It is preferably a sulfonic acid group that is directly or bonded to the pigment skeleton through an alkyl group, an aryl group, a heterocyclic group, or the like. In addition, these substituents may be substituted in plural in one pigment skeleton.

之磺酸衍生物等。該等可單獨使用1種，亦可併用2種以上。 Specific examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolo Sulfonic acid derivatives of pyrrole, two

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

(4) Photoacid generator

The so-called photoacid generator refers to a compound that can generate an acid by ultraviolet rays, and the crosslinking reaction is carried out by the action of the acid generated during exposure, for example, in the presence of a crosslinking agent such as a melamine compound.

、2-(4-甲氧基苯基)-4,6-雙三氯甲基三

等三

化合物等，但並不限於此。 In this photoacid generator, the solubility to a solvent, especially the solubility to the solvent used for a photosensitive coloring composition, is preferable. For example, diphenyl iodonium, xylyl iodonium, phenyl(p-anisyl) iodonium, bis(m-nitrophenyl) iodonium, bis(p-tert-butylphenyl) iodonium, bis(p-chlorobenzene) base) iodonium, bis(n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium and other diaryl iodonium, or triphenyl iodonium Chloride, bromide, fluoroboride, hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis(pentafluorophenyl)borate, etc., or diphenyl Perinium organoboron complexes such as benzalkonium methyl pernium (n-butyl) triphenyl borate, or 2-methyl-4,6-bistrichloromethyltriphenyl

, 2-(4-methoxyphenyl)-4,6-bistrichloromethyltris

wait three

compounds, etc., but not limited thereto.

(5) Cross-linking agent

In the photosensitive coloring composition of this invention, a crosslinking agent can be added further, for example, a melamine or a melamine-based compound can be used. As these crosslinking agents, for example, melamine or melodiamine-based compounds represented by the following general formula (6) can be mentioned.

[Chemical 28]

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

Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and an alkyl group, an alkoxy group, or a halogen atom may be bonded to the phenyl group or the naphthyl group. and other substituents. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group among the above, especially a methyl group.

The melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1) includes hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, Pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, etc.

[Chemical 29]

In formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents - CH ₂ OR ⁶⁸ group, the rest R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or -CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents a hydrogen atom or an alkyl group .

In addition, the melamine-based compound corresponding to the general formula (6), that is, the compound in which R ⁶¹ in the general formula (6) is an aryl group, includes tetramethylolbenzomelamine, tetramethoxy methyl benzo melamine, trimethoxymethyl benzo melamine, tetraethoxy methyl benzo melamine, etc.

Furthermore, the crosslinking agent which has a methylol group or a methylol alkyl ether group can also be used. Examples are listed below.

-2-酮(通稱N-乙基二羥甲基三

酮)或其二甲醚體、二羥甲基三亞甲基脲或其二甲醚體、3,5-雙(羥基甲基)全氫-1,3,5-

二

-4-酮(通稱二羥甲基脲)或其二甲醚體、四羥甲基乙二醛二烷基脲或其四甲醚體。 2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl) ) perhydro-1,3,5-tri

-2-keto (commonly known as N-ethyl dimethylol tris

ketone) or its dimethyl ether form, dimethylol trimethylene urea or its dimethyl ether form, 3,5-bis(hydroxymethyl)perhydro-1,3,5-

two

-4-ketone (commonly known as dimethylol urea) or its dimethyl ether form, tetramethylolglyoxal dialkyl urea or its tetramethyl ether form.

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

(6) Sulfhydryl compounds

As a polymerization accelerator, a mercapto compound may also be added in order to improve the adhesion to the substrate.

唑、2-巰基苯并咪唑、己二硫醇、癸二硫醇、1,4-二甲基巰基苯、丁二醇雙巰基丙酸酯、丁二醇雙巰基乙酸酯、乙二醇雙巰基乙酸酯、三羥甲基丙烷三巰基乙酸酯、丁二醇雙統基丙酸酯、三羥甲基丙烷三巰基丙酸酯、三羥甲基丙烷三巰基乙酸酯、季戊四醇四巰基丙酸酯、季戊四醇四巰基乙酸酯、三羥基乙基三巰基丙酸酯、乙二醇雙(3-巰基丁酸酯)、丁二醇雙(3-巰基丁酸酯)、1,4-雙(3-統基丁醯氧基)丁烷、三羥甲基丙烷三(3-巰基丁酸酯)、季戊四 醇四(3-巰基丁酸酯)、季戊四醇三(3-巰基丁酸酯)、乙二醇雙(3-巰基異丁酸酯)、丁二醇雙(3-巰基異丁酸酯)、三羥甲基丙烷三(3-巰基異丁酸酯)、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮等具有雜環之巰基化合物或脂肪族多官能基巰基化合物等。該等可單獨使用1種各種巰基化合物，或者將2種以上混合而使用。 Examples of the type of mercapto compound include: 2-mercaptobenzothiazole, 2-mercaptobenzothiazole

azole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis-mercaptopropionate, butanediol bis-thioglycolate, ethylene glycol Bis-mercaptoacetate, Trimethylolpropane Trimercaptoacetate, Butylene Glycol Bis-Propionate, Trimethylolpropane Trimercaptopropionate, Trimethylolpropane Trimercaptoacetate, Pentaerythritol Tetramercaptopropionate, Pentaerythritol Tetramercaptoacetate, Trihydroxyethyl Trimercaptopropionate, Ethylene Glycol Bis(3-Mercaptobutyrate), Butylene Glycol Bis(3-Mercaptobutyrate), 1 ,4-bis(3-tributanoyloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate) ester), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1, 3,5-Tris(3-mercaptobutoxyethyl)-1,3,5-tris

-2,4,6(1H,3H,5H)-triketone and other mercapto compounds or aliphatic polyfunctional mercapto compounds having a heterocyclic ring. These various mercapto compounds can be used individually by 1 type, or can be used in mixture of 2 or more types.

<The amount of ingredients in the photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, the content of the (a) colorant is usually 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass relative to the total solid content in the photosensitive coloring composition. mass % or more. Moreover, 60 mass % or less is normally preferable, and 50 mass % or less is more preferable.

By making the content of (a) the colorant more than the above-mentioned lower limit value, a sufficient optical density (OD) tends to be obtained; and by making the content of the colorant less than or equal to the above-mentioned upper limit value, it is easy to obtain sufficient plate-making characteristics. tendency.

Furthermore, in the first aspect and the fourth aspect, at least one pigment selected from the group consisting of a red pigment and an orange pigment is preferably 1 part by mass or more relative to 100 parts by mass of the (a) colorant, More preferably, it is 2 parts by mass or more, and still more preferably 3 parts by mass or more. Moreover, 30 mass parts or less are preferable, 20 mass parts or less are more preferable, 15 mass parts or less are still more preferable, 10 mass parts or less are still more preferable, 7 mass parts or less are especially preferable. By setting it as the said lower limit or more, sufficient optical density (OD) tends to be obtained, and by setting it as below the said upper limit, there exists a tendency for a plate-making characteristic to be ensured.

Moreover, in the 1st aspect and the 4th aspect, with respect to (a) 100 parts by mass of the colorant, at least one pigment selected from the group consisting of a blue pigment and a violet pigment It is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, and most preferably 65 parts by mass or more . Moreover, 90 mass parts or less are preferable, 80 mass parts or less are more preferable, 75 mass parts or less are still more preferable, and 70 mass parts or less are especially preferable. By making it more than the said lower limit value, there exists a tendency for the light-shielding property to be ensured, and there exists a tendency for the plate-making characteristic to be able to be ensured by setting it as below the said upper limit value.

Moreover, in the second aspect, the content of the organic black pigment represented by the general formula (1) with respect to 100 parts by mass of the colorant (a) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further It is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, particularly preferably 60 parts by mass or more, and most preferably 70 parts by mass or more. Moreover, 95 mass parts or less are preferable, 90 mass parts or less are more preferable, 85 mass parts or less are still more preferable, and 80 mass parts or less are especially preferable. By setting it as the said lower limit or more, there exists a tendency for the light-shielding property to be improved, and by setting it as below the said upper limit, it exists in the tendency which can suppress the fall of reliability.

Moreover, in the third aspect, the organic pigment is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, preferably 60 parts by mass or more, with respect to 100 parts by mass of the (a) colorant. 70 parts by mass or more. Moreover, it is preferably 99 parts by mass or less, more preferably 95 parts by mass or less, still more preferably 90 parts by mass or less, particularly preferably 85 parts by mass or less, and most preferably 80 parts by mass or less. By making it more than the said lower limit value, there exists a tendency for a plate-making characteristic to be able to be ensured, and there exists a tendency for sufficient optical density (OD) to be obtained by making it into the said upper limit value or less.

Furthermore, in the third aspect, at least one pigment selected from the group consisting of a red pigment and an orange pigment is preferably 0 parts by mass or more, more preferably 1 mass part, relative to 100 parts by mass of the colorant (a). part or more, more preferably 2 parts by mass or more. again, It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 0 parts by mass. By setting it as the said lower limit or more, sufficient optical density (OD) tends to be obtained, and by setting it as below the said upper limit, there exists a tendency for a plate-making characteristic to be ensured.

Furthermore, in the third aspect, at least one pigment selected from the group consisting of blue pigments and violet pigments is preferably 20 parts by mass or more, more preferably 30 parts by mass relative to 100 parts by mass of the colorant (a). It is more preferably 40 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, and most preferably 65 parts by mass or more. Moreover, 90 mass parts or less are preferable, 85 mass parts or less are more preferable, and 80 mass parts or less are still more preferable. By making it more than the said lower limit value, there exists a tendency for the light-shielding property to be ensured, and there exists a tendency for the plate-making characteristic to be able to be ensured by setting it as below the said upper limit value.

When (a) the colorant contains an organic black pigment, the amount of the organic black pigment is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 20 parts by mass relative to 100 parts by mass of the (a) colorant copies or more. Moreover, 50 mass parts or less are preferable, 40 mass parts or less are more preferable, 30 mass parts or less are further more preferable, and 20 mass parts or less are especially preferable. By setting it as the said lower limit or more, sufficient optical density (OD) tends to be obtained, and by setting it as below the said upper limit, there exists a tendency for a plate-making characteristic to be ensured.

When (a) the colorant contains carbon black, the amount of carbon black is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more relative to 100 parts by mass of the (a) colorant , particularly preferably 20 parts by mass or more. Moreover, 50 mass parts or less are preferable, 40 mass parts or less are more preferable, 35 mass parts or less are still more preferable, and 30 mass parts or less are still more preferable. By setting the above lower limit value or more, a sufficient optical density (OD) tends to be obtained, and by setting the above upper limit value or less, it is possible to ensure the The tendency of version characteristics.

(b) The content ratio 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. 25 mass % or more, especially 30 mass % or more are preferable. Usually 85 mass % or less, preferably 80 mass % or less, more preferably 70 mass % or less, still more preferably 60 mass % or less, still more preferably 50 mass % or less, particularly preferably 40 mass % or less.

By making content of (b) alkali-soluble resin more than the said lower limit, the fall of the solubility in a developing solution of an unexposed part can be suppressed, and there exists a tendency for development failure to be suppressed. Moreover, by setting it below the said upper limit, it exists in the tendency which can suppress that the penetration of a developing solution with respect to an exposure part becomes high, and the sharpness or adhesiveness of a pixel can be suppressed from falling.

(c) The content ratio 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, more preferably 1% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. Preferably it is 2 mass % or more, More preferably, it is 3 mass % or more, More preferably, it is 4 mass % or more. It is usually 15 mass % or less, preferably 10 mass % or less, more preferably 8 mass % or less, and still more preferably 7 mass % or less.

By making the content ratio of the (c) photopolymerization initiator more than or equal to the above lower limit value, there is a tendency that the decrease in sensitivity can be suppressed; The solubility of the product is reduced and the tendency of poor development is suppressed.

(c) The content ratio 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 50 mass % or more, more preferably 70 mass % or more 90 mass % or more is particularly preferable, and usually 100 mass % or less. By making it more than the said lower limit, the surface smoothness of the hardened|cured material obtained tends to become favorable.

When a polymerization accelerator is used together with the (c) photopolymerization initiator, the content ratio of the polymerization accelerator is preferably 0.05 mass % or more with respect to the total solid content of the photosensitive coloring composition of the present invention, and is usually 10 mass % or less, preferably 5 mass % or less, the ratio of the polymerization accelerator to 100 mass parts of the (c) photopolymerization initiator is usually preferably 0.1 to 50 mass parts, especially 0.1 to 20 mass parts use.

By making the content ratio of the polymerization accelerator more than the above-mentioned lower limit value, the tendency to reduce the sensitivity to exposure light can be suppressed; by making the content ratio of the polymerization accelerator less than or equal to the above-mentioned upper limit value, the unexposed part in the developing solution can be suppressed. The solubility of the product is reduced and the tendency of poor development is suppressed. Moreover, about the compounding ratio which the sensitizing dye occupies in the photosensitive coloring composition of this invention, from the viewpoint of sensitivity, in the total solid content in the photosensitive coloring composition, it is preferable that it is usually 20 mass % or less. It is 15 mass % or less, More preferably, it is 10 mass % or less.

(d) The content rate of an ethylenically unsaturated compound is 30 mass % or less normally with respect to the total solid content of the photosensitive coloring composition of this invention, Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less. By making the content ratio of (d) ethylenically unsaturated compound below the said upper limit value, it exists in the tendency which can suppress that the permeability|transmittance of a developer with respect to an exposure part becomes high, and becomes easy to obtain a favorable image. In addition, the lower limit value of the content ratio of the (d) ethylenically unsaturated compound is usually 1 mass % or more, preferably 5 mass % or more.

Furthermore, by using the (e) solvent, 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 A liquid is prepared so that it may be 30 mass % or less.

(f) The content rate of a dispersing agent is 1 mass % or more normally in the solid content of a photosensitive coloring composition, Preferably it is 3 mass % or more, More preferably, it is 5 mass % or more. Moreover, it is usually 30 mass % or less, Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less, More preferably, it is 10 mass % or less.

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

By setting the content ratio of the (f) dispersant to the above lower limit value or more, sufficient dispersibility tends to be easily obtained; by setting it to the above upper limit value or less, the ratio of other components can be relatively reduced. In addition, the tendency to decrease in sensitivity, plate-making properties, etc. is suppressed.

In the case of using an adhesion improving agent, its content ratio is usually 0.1 to 5 mass %, preferably 0.2 to 3 mass %, and more preferably 0.4 to 2 mass % with respect to the total solid content in the photosensitive coloring composition. . By setting the content ratio of the adhesion improving agent to be more than the above lower limit value, the effect of improving the adhesion tends to be sufficiently obtained; Tendency to become a condition of defect.

Moreover, when using a surfactant, its content rate is 0.001-10 mass % normally with respect to the total solid content in the photosensitive coloring composition, Preferably it is 0.005-1 mass %, More preferably, it is 0.01-0.5 % by mass, preferably 0.03 to 0.3% by mass. By making the content of the surfactant more than the above-mentioned lower limit value, the smoothness and uniformity of the coating film tend to be easily expressed; by making the content of the surfactant less than or equal to the above-mentioned upper limit value, the smoothness of the coating film is likely to be expressed. , uniformity, and also inhibit the tendency of other characteristics to deteriorate.

<Physical properties of photosensitive coloring composition>

The photosensitive coloring composition of this invention can be used suitably for forming a coloring spacer, and it is preferable to be black from a viewpoint of being used as a coloring spacer. Moreover, the optical density (OD) per 1 micrometer of the film thickness of the coating film is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.5 or more, particularly preferably 1.8 or more. Usually, it is 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less.

<The manufacturing method of the photosensitive coloring composition>

The photosensitive coloring composition of the present invention (hereinafter, sometimes referred to as "photoresist") is produced according to a conventional method. Usually, the (a) colorant is preferably dispersed in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. The (a) colorant is made into fine particles by the dispersion treatment, so that the coating properties of the photoresist are improved.

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

In this way, in the step of producing a photoresist, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) organic solvent, and (f) dispersant usable in the pigment dispersion liquid, those described as usable in the photosensitive coloring composition can be preferably used, respectively.

Furthermore, in the case of dispersing the liquid containing the total components for preparing the photosensitive coloring composition, there is a high degree of reflection due to the heat generated during the dispersing process. Possibility of modification of reactive components. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersant.

In the case of dispersing the (a) colorant with a sand mill, it is preferable to use glass beads or zirconia beads with a particle size of about 0.1 to 8 mm. Regarding the dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, and preferably in the range of room temperature to 80°C. The dispersing time varies with the composition of the liquid and the size of the dispersing treatment device. Therefore, it needs to be adjusted appropriately. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photoresist is in the range of 50~300.

When the glossiness of the photoresist is low, the dispersion treatment is not sufficient, and the coarse pigment (color material) particles remain in many cases, and the developability, adhesion, resolution, etc. may become insufficient. In addition, if the dispersion treatment is performed until the gloss value exceeds the above-mentioned range, the pigment will be crushed and a large number of ultrafine particles will be generated, so that the dispersion stability tends to be impaired on the contrary.

In addition, the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, which is measured by a dynamic light scattering method or the like.

Next, the ink obtained by the above-mentioned dispersion treatment is mixed with the above-mentioned other components contained in the photoresist to prepare a uniform solution. In the photoresist manufacturing step, fine dirt is often mixed into the liquid, so it is preferable to filter the obtained photoresist with a filter or the like.

[hardened product]

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

[coloring spacer]

Next, the coloring spacer using the photosensitive coloring composition of this invention is demonstrated based on the manufacturing method.

(1) Support body

The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, and as a material, for example, polyester-based resins such as polyethylene terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polysilicon are exemplified. Thermoplastic resin sheets such as epoxy resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic resins, and various glasses.

Among them, from the viewpoint of heat resistance, glass and heat-resistant resin are preferred. In addition, there are cases in which transparent electrodes such as indium tin oxide (ITO, Indium Tin Oxide) and indium zinc oxide (IZO, Indium Zinc Oxide) are formed on the surface of the substrate. In addition to the transparent substrate, it can also be formed on the TFT array.

In order to improve surface physical properties such as adhesion, the support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, or film forming treatment of various resins such as urethane resins, etc., if necessary. The thickness of the transparent substrate is usually set to 0.05 to 10 mm, preferably within the range of 0.1 to 7 mm. Moreover, when performing the film forming process of various resin, the film thickness is normally 0.01-10 micrometers, Preferably it is the range of 0.05-5 micrometers.

(2) Colored spacers

The photosensitive coloring composition of the present invention is used with a known color filter The same application as the photosensitive coloring composition. Hereinafter, the case of using as a coloring spacer (black photosensitive spacer) is demonstrated based on the specific example of the formation method of the black photosensitive spacer using the photosensitive coloring composition of this invention.

Usually, the photosensitive coloring composition is supplied in the form of a film or a pattern by a method such as coating on the substrate on which the black photosensitive spacer should be provided, and the solvent is dried. Then, pattern formation is performed by methods, such as the photolithography method which performs exposure-development. After that, additional exposure or thermosetting treatment is performed as necessary, whereby black photosensitive spacers are formed on the substrate.

(3) Formation of coloring spacers

[1] Supply method to substrate

The photosensitive coloring composition of this invention is normally supplied to a board|substrate in the state which melt|dissolved or disperse|distributed in a solvent. As the supply method, it can be performed by a conventionally known method, for example, a spin coater method, a wire bar coating method, a flow coating method, a die nozzle coating method, a roll coating method, a spray coating method, or the like. In addition, it can also be supplied in a pattern by an ink jet method, a printing method, or the like.

Among them, if the die coating method is used, the usage amount of the coating liquid is greatly reduced, the influence of mist and the like adhering in the spin coating method is completely eliminated, and the generation of foreign matter is suppressed from a comprehensive viewpoint. better.

The coating amount varies depending on the application. For example, in the case of a black photosensitive spacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. In addition, it is important that the dry film thickness or the height of the spacer to be finally formed is uniform over the entire area of the substrate. When the difference is large, uneven defects will be generated in the liquid crystal panel.

However, when using the photosensitive coloring composition of the present invention, In the case of forming black photosensitive spacers with different heights at one time, the heights of the finally formed black photosensitive spacers are different.

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

[2] Drying method

The drying after supplying the photosensitive coloring composition solution on the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, it is also possible to combine a drying method under reduced pressure in which drying is performed in a reduced pressure chamber without raising the temperature.

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

[3] Exposure method

Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet light or visible light through the mask pattern. In the case of exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or disposing the exposure mask at a position away from the coating film of the photosensitive coloring composition can also be used. And a method of projecting the exposure light through the exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern can also be used.

At this time, in order to prevent the reduction of the sensitivity of the photopolymerizable layer due to oxygen as necessary, it may be performed in a deoxidized environment, or polyethylene may be formed on the photopolymerizable layer. Exposure is performed after an oxygen barrier layer such as an alcohol layer.

As a preferred aspect of the present invention, in the case of simultaneously forming black photosensitive spacers with different heights by photolithography, for example, a light-shielding portion (light transmittance of 0%) and a plurality of openings are used. It is the exposure mask of the opening with the highest average light transmittance (completely penetrating opening) having the smaller average light transmittance (intermediate penetrating opening). With this method, the difference in residual film ratio is generated by the difference in average light transmittance between the intermediate penetration opening and the complete penetration opening, that is, the difference in exposure amount.

For example, a method of forming the intermediate penetration opening by a matrix-like light-shielding pattern having minute polygonal light-shielding cells is known. In addition, a method of controlling light transmittance by a film of materials such as chromium-based, molybdenum-based, tungsten-based, and silicon-based materials as absorbers is known.

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

As an optical filter, for example, a thin film can be used to control the light transmittance of the exposure wavelength. As a material in this case, for example, Cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.) , MoSi, Si, W, Al, etc.

The exposure amount is usually 1 mJ/cm ² or more, preferably 5 mJ/cm ² or more, more preferably 10 mJ/cm ² or more, usually 300 mJ/cm ² or less, preferably 200 mJ/cm ² or less, more preferably 150mJ/ ^cm2 or less. In addition, 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, and more preferably 75 μm or more. Moreover, it is 500 micrometers or less normally, Preferably it is 400 micrometers or less, More preferably, it is 300 micrometers or less.

[4] Development method

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

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic basic compounds, or single. Double or triethanolamine, single. Double or trimethylamine, single. Double or triethylamine, single or double isopropylamine, n-butylamine, single. Di or triisopropanolamine, ethyleneimine, ethylenediimide, tetramethylammonium hydroxide (TMAH), choline and other organic basic compounds. These basic compounds may be a mixture of two or more kinds.

Examples of the above-mentioned surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters Nonionic surfactants such as alkanes; anionic interfaces such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates Active agents; amphoteric surfactants such as alkyl betaines and amino acids.

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

The conditions of the development treatment are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C, preferably 15 to 45 ° C, and particularly preferably 20 to 40 ° C. The development method can be immersion development method, spray development method, Either a magnetic brush development method, an ultrasonic development method, or the like.

[5] Additional exposure and thermal curing

The substrate after the development may be additionally exposed by the same method as the above-mentioned exposure method if necessary, and a thermal curing treatment may also be performed. Regarding the thermal curing conditions at this time, the temperature is selected within the range of 100°C to 280°C, preferably 150°C to 250°C, and the time is selected within the range of 5 minutes to 60 minutes.

The size or shape of the coloring spacer of the present invention is appropriately adjusted according to the specifications of the color filter to which the coloring spacer is applied. It is more useful in the case of a black photosensitive spacer having a height different from that of the sub-spacer. In this case, the height of the spacer is usually about 2-7 μm, and the sub-spacer has a height that is usually about 0.2-1.5 μm lower than that of the spacer. .

Moreover, about the optical density (OD) per 1 micrometer of the coloring spacer of this invention, from a light-shielding viewpoint, 1.2 or more are preferable, 1.5 or more are more preferable, 1.8 or more are more preferable. Moreover, it is 4.0 or less normally, Preferably it is 3.0 or less. Here, the optical density (OD) is a value measured by the following method.

[color filter]

The color filter of the present invention has the coloring spacer of the present invention as described above. For example, black matrix, red, green, A blue pixel coloring layer and a protective layer are formed into coloring spacers, and then an alignment film is formed and manufactured.

A liquid crystal cell is formed by laminating the color filter with the coloring spacer of the present invention and the liquid crystal driving side substrate, and injecting liquid crystal into the formed liquid crystal cell, whereby a liquid crystal with the coloring spacer of the present invention can be produced Video display devices such as display devices.

Example

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

<Organic black pigment>

Irgaphor (registered trademark) Black S 0100 CF (with a chemical structure represented by the following formula (2)) manufactured by BASF Corporation

[Chemical 30]

<Alkali-Soluble Resin-I>

It heated up to 120 degreeC, stirring 145 mass parts of propylene glycol monomethyl ether acetates with nitrogen substitution. At this time, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and 3 parts by mass were added. 2,2'-azobis-2- 8.47 parts by mass of methyl butyronitrile, and further stirring was continued at 90° C. for 2 hours. Next, the inside of the reaction container was changed to air replacement, 0.7 parts by mass of tris-dimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were charged into 43.2 parts by mass of acrylic acid, and the reaction was continued at 100° C. for 12 hours. Then, 56.2 mass parts of tetrahydrophthalic anhydride (THPA) and 0.7 mass parts of triethylamine were added, and it was made to react at 100 degreeC for 3.5 hours. The alkali-soluble resin-I obtained in this way had a weight-average molecular weight Mw determined by GPC of about 8400, and an acid value of 80 mgKOH/g.

<Alkali-Soluble Resin-II>

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

<Dispersant-I>

"DISPERBYK-LPN21116" manufactured by BYK-Chemie (comprising A block with quaternary ammonium salt group and tertiary amine group in side chain and B block without quaternary ammonium salt group and amine group) Stage copolymer. Amine value is 70mgKOH/g. Acid value is less than 1mgKOH/g.)

The A block of the dispersant-I contains repeating units of the following formulae (1a) and (2a), and the B block contains the repeating unit of the following formula (3a). The content ratios of the repeating units of the following formulae (1a), (2a), and (3a) to the total repeating units of Dispersant-I were 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[Chemical 31]

<Dispersant-II>

"DISPERBYK-167" (urethane polymer dispersant) manufactured by BYK-Chemie

<Pigment Derivatives>

"Solsperse 12000" manufactured by Lubrizol Corporation

<Solvent-I>

PGMEA: Propylene Glycol Monomethyl Ether Acetate

<Solvent-II>

MB: 3-ethoxybutanol

<Photopolymerization Initiator-I>

Irgacure OXE03 (manufactured by BASF)

[Chemical 32]

<Photopolymerization Initiator-II>

[Chemical 33]

<Photopolymerization Initiator-III>

[Chemical 34]

<Photopolymerizable monomer>

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

<additional agent>

KAYAMER PM-21 (containing methacrylic acid) manufactured by Nippon Kayaku Co., Ltd. Acyl phosphate)

<Surfactant>

MEGAFAC F-559 manufactured by DIC Corporation

<Evaluation of Optical Density (OD)>

Optical density (OD) was measured with a transmission densitometer ("D200-II" manufactured by GretagMacbeth). Furthermore, the film thickness at the measurement site was also measured, and the optical density (unit OD) per unit film thickness (1 μm) was calculated.

<Evaluation of substrate adhesion>

The value of the opening diameter (μm) of the smallest opening diameter among those whose resolution is good and the pattern remains on the substrate is set to be the smallest close contact. The smaller the value is, the more excellent the substrate adhesion is.

<Evaluation of Surface Smoothness>

Regarding the pattern to be the subject, it was observed by an optical microscope in a field of view of 70 μm×70 μm whether or not a wrinkle occurred on the surface after heating. In addition, the evaluation criteria are as follows.

○: No micron-level wrinkles are observed on the pattern surface

×: The micron-level wrinkles on the pattern surface are very obvious

<Evaluation of surface roughness>

For the pattern to be the subject, the surface roughness Sa (arithmetic mean roughness Sa (arithmetic mean roughness) was measured in a focusing mode in a field of view of 70 μm × 70 μm by using Micromap, a three-dimensional non-contact surface shape measuring system of Ryoka Systems Co., Ltd., using an optical lens of 50 times magnification. degrees, nm).

<Preparation of Pigment Dispersion Liquid 1>

之氧化鋯珠作為珠粒，並添加分散液之2.5倍之質量。分散結束後，藉由過濾器將珠粒與分散液分離而製備顏料分散液1。 The pigments, dispersing agents, dispersing aids, alkali-soluble resins, and solvents described in Table 1 were mixed so as to have the mass ratios described in Table 1. The solution was dispersed in the range of 25 to 45°C for 3 hours by means of a paint shaker. Use 0.5mm

The zirconia beads were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads were separated from the dispersion by a filter to prepare Pigment Dispersion 1 .

[Table 1]

<Preparation of Pigment Dispersions 2 and 3>

Pigment Dispersion Liquid 2 was prepared in the same manner as Pigment Dispersion Liquid 1, except that the pigments, dispersants, dispersing aids, alkali-soluble resins, and solvents described in Table 1 were mixed in the mass ratios described in Table 1. and 3.

<Pigment Dispersion Liquid 4 (Coated Carbon Black Dispersion Liquid)>

Carbon black is produced by the usual oil furnace method. Among them, as the raw material oil, Na, Coking coal furnace gas is used for ethylene base oil with less Ca and S content. Furthermore, as the reaction stop water, pure water treated with an ion exchange resin was used. Using a homogenizer, 540 g of the obtained carbon black and 14,500 g of pure water were stirred together at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container with a screw mixer, and 600 g of toluene in which 60 g of epoxy resin "Epikote 828" (manufactured by Mitsubishi Chemical Co., Ltd.) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the carbon black dispersed in water all moved to the toluene side and became particles of about 1 mm.

Next, after throwing off water with a 60-mesh metal mesh, it was put into a vacuum dryer and dried at 70° C. for 7 hours to completely remove toluene and water. The obtained coated carbon black, a dispersant, a pigment derivative, and a solvent were mixed so that the mass ratio described in Table 2 might be obtained.

之氧化鋯珠作為珠粒，並添加與分散液相同之質量。分散結束後，藉由過濾器將珠粒與分散液分離而製備。 It is premixed by stirring it well with a mixer. Next, the dispersion treatment is carried out in the range of 25~45℃ for 6 hours by a paint mixer. Use 0.5mm

The zirconia beads were used as beads, and the same mass as the dispersion was added. After the dispersion is completed, the beads are prepared by separating the beads from the dispersion by a filter.

[Examples 1 and 2, Comparative Examples 1 to 3]

Using the pigment dispersion liquids 1 to 4 prepared above, each component was added so that the proportions in Table 2 would be adjusted, and then PGMEA was added so that the solid content would be 22% by mass and stirred to dissolve to prepare a photosensitive coloring composition. . Using the obtained photosensitive coloring composition, it evaluated by the following method. In addition, the value of the upper row in Table 2 represents the usage-amount of each component. On the other hand, the value of the lower row shows the solid content of each component by the content ratio with respect to the total solid content of the photosensitive coloring composition.

[Table 2]

<One-time formation method of hardened objects with different heights>

Each photosensitive coloring composition was apply|coated on the glass substrate ("AN100" by AGC company) using a spin coater. Next, the coating film was formed by heating and drying on a hot plate at 100° C. for 70 seconds. For the obtained coating film, completely penetrating openings with circular patterns of 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 diameters of 5 to 50 μm ( 5~20μm: every 1μm; 25μm~50μm: every 5μm), the middle penetrating openings of circular patterns of various diameters, and the exposure treatment using the exposure mask with the straight openings (completely penetrating) with a width of 100 μm . The middle penetration opening is a thin film of Cr oxide, and the transmittance at a wavelength of 365 nm is set to 10±2%. The exposure gap (distance between the mask and the coated surface) was 220 μm. As irradiation light, ultraviolet rays with an intensity of 32 mW/cm ² at a wavelength of 365 nm were used, and the exposure amount was set to 100 mJ/cm ² . In addition, ultraviolet irradiation is performed in the air.

Next, using a developer containing an aqueous solution containing 0.05 mass % of potassium hydroxide and 0.08 mass % of a nonionic surfactant (“A-60” manufactured by Kao Corporation), a water pressure of 0.15 MPa was carried out at 25° C. After the shower development, the development was stopped with pure water and washed with water jet. The spray developing time was adjusted between 10 and 120 seconds, and was set to 1.5 times the time for dissolving and removing the unexposed coating film. Through these operations, a pattern from which redundant portions have been removed is obtained. The substrate on which the pattern was formed was heated in an oven at 230° C. for 20 minutes to harden the pattern to obtain a substantially cylindrical spacer pattern.

The optical density (OD) per unit film thickness (1 μm) of the pattern corresponding to the above-mentioned linear openings was measured by the above-mentioned method. Moreover, in the complete penetration opening part of the circular pattern of 5-50 micrometers, and the pattern corresponding to the intermediate penetration opening part of 5-50 micrometers, the evaluation of the board|substrate adhesiveness was performed by the said method. Furthermore, about the pattern corresponding to the said linear opening part, the surface smoothness evaluation was performed by the said method. Moreover, about the pattern corresponding to the said linear opening part, the surface roughness evaluation was performed by the said method. 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 high unit OD, excellent light-shielding properties, and excellent surface smoothness. Moreover, the substrate adhesiveness of the intermediate penetration opening was also favorable. On the other hand, it was confirmed that Comparative Examples 1 to 3 and The values of the unit OD of Examples 1 and 2 are the same, but the surface smoothness is poor, and the adhesion between the substrates through the opening in the middle is poor.

Generally, in order to improve the light-shielding property of a coloring spacer, the method of raising a pigment density|concentration, or the method of using together the pigment with high light-shielding property is known. However, it is considered that if such a method is applied, the UV transmittance decreases, a difference in crosslinking density occurs in the film thickness direction, the crosslinking density on the surface of the film becomes higher than that at the bottom of the film, and the thermal shrinkage due to the thermal curing process is considered. On the other hand, wrinkles are generated on the film surface, and the surface smoothness is deteriorated.

In the photosensitive coloring composition of the present invention, since the oxime ester compound represented by the above-mentioned formula (I) is used as a photopolymerization initiator, it is considered that the compound is easily absorbed into the film due to the halogen atom in the chemical structure of the compound. Distributing the initiator near the surface prevents the crosslinking density of the film surface from becoming excessively high due to the influence of oxygen barrier, which can reduce the generation of wrinkles on the film surface caused by thermal shrinkage during the thermal curing process.

In addition, it is considered that the absorption of long-wavelength light increases due to the naphthalene ring in the carbazole skeleton of the compound, and the long-wavelength light contained in the ultraviolet lamp can also be used to increase the crosslinking density near the bottom of the film. The substrate adhesion also becomes good in the pattern formed by the opening part with a low penetration rate like the intermediate penetration opening part.

[Example 3 and Comparative Example 4]

Using the above-prepared pigment dispersions 3 and 4, each component was added in such a way that the ratio in the solid content became the compounding ratio of Table 3, and then PGMEA was added in such a way that the solid content became 22% by mass and stirred to dissolve, thereby preparing Photosensitive coloring composition. Using the obtained photosensitive coloring composition, except that the exposure amount in the exposure process was made into 40 mJ/cm< ² >, it evaluated by the same procedure as Example 1. In addition, the value of the upper row in Table 3 represents the usage-amount of each component. On the other hand, the value of the lower row shows the solid content of each component by the content ratio with respect to the total solid content of the photosensitive coloring composition. In addition, the visual field of the evaluation of surface smoothness was set to 5 cm x 5 cm.

[table 3]

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. Moreover, the substrate adhesiveness of the intermediate penetration opening was also favorable. On the other hand, it was confirmed that Comparative Example 4 had the same unit OD value as Example 3, but the surface smoothness was poor, the surface roughness value was also large, and the substrate adhesion at the intermediate penetration opening was poor.

The present invention will be described in detail using specific aspects, and it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the intent and scope of the present invention. Furthermore, this application is based on the Japanese patent application filed on March 11, 2015 (Japanese Patent Application No. 2015-048577) and the Japanese Patent Application filed on March 11, 2015 (Japanese Patent Application No. 2015-048578 ). ), and the date of application on August 7, 2015 Japanese Patent Application (Japanese Patent Application No. 2015-157456), the entire contents of which are incorporated by reference.

(Industrial Availability)

According to the photosensitive coloring composition of the present invention, a cured product and a coloring spacer having high light-shielding properties and excellent surface smoothness can be provided, and further, an image display device having such a coloring spacer can be provided. Accordingly, the present invention has extremely high industrial applicability in various fields of photosensitive coloring compositions, cured products, coloring spacers, and image display devices.

Claims (11)

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, characterized in that the colorant (a) 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 ; and the above-mentioned (c) photopolymerization initiator comprises an oxime ester compound represented by the following formula (I),

(In the above general formula (I), R ¹ represents an aromatic ring group which may have a substituent, R ² represents an alkane group which may have a substituent or an aryl group which may have a substituent, R ³ represents a hydrogen atom, or an alkyl group which may have a substituent, R ⁴ represents an aromatic ring group which may have a substituent, R ⁵ and R ⁶ independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, wherein, At least any one of R ⁵ and R ⁶ is a naphthalene ring that may have a substituent, and at least one of R ¹ and R ⁴ has a -OR ⁷ group as a substituent, wherein R ⁷ represents a haloalkyl group, and X represents a direct bond or carbonyl, Z represents a direct bond or carbonyl). As claimed in the photosensitive coloring composition of claim 1, wherein, is selected from The content ratio of at least one pigment in the group consisting of the red pigment and the orange pigment is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the above-mentioned (a) colorant. The photosensitive coloring composition according to claim 1, wherein the content ratio of at least one pigment selected from the group consisting of a blue pigment and a violet pigment is 20 parts by mass or more relative to 100 parts by mass of the (a) colorant and 90 parts by mass or less. The photosensitive coloring composition according to claim 2, wherein the content ratio of at least one pigment selected from the group consisting of a blue pigment and a violet pigment is 20 parts by mass or more relative to 100 parts by mass of the (a) colorant and 90 parts by mass or less. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the (a) colorant contains an organic black pigment. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the (a) colorant contains carbon black. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the optical density per 1 μm of the film thickness of the coating film after curing is 1.0 or more. The photosensitive coloring composition according to any one of claims 1 to 4, which is used to form coloring spacers having different heights at one time by photolithography. A cured product obtained by curing the photosensitive coloring composition of any one of claims 1 to 8. A colored spacer formed from the hardened material of claim 9. An image display device including the coloring spacer of claim 10.